Picolinamides as fungicides

ABSTRACT

This disclosure relates to picolinamides of Formula I and their use as fungicides.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a U.S. National Phase filing of International Application No. PCT/US2015/067206, filed Dec. 21, 2015, which claims the benefit of U.S. Provisional Patent Application Serial Nos. 62/098,089 filed Dec. 30, 2014, 62/098,097 filed Dec. 30, 2014, 62/255,163 filed Nov. 13, 2015 and 62/255,168 filed Nov. 13, 2015, the disclosures of which are hereby expressly incorporated by reference herein in their entirety.

BACKGROUND & SUMMARY

Fungicides are compounds, of natural or synthetic origin, which act to protect and/or cure plants against damage caused by agriculturally relevant fungi. Generally, no single fungicide is useful in all situations. Consequently, research is ongoing to produce fungicides that may have better performance, are easier to use, and cost less.

The present disclosure relates to picolinamides and their use as fungicides. The compounds of the present disclosure may offer protection against ascomycetes, basidiomycetes, deuteromycetes and oomycetes.

One embodiment of the present disclosure may include compounds of Formula I:

X is hydrogen or C(O)R₅;

Y is hydrogen, C(O)R₅, or Q;

Q is

R₁ and R₁₁ are independently chosen from hydrogen or alkyl, optionally substituted with 0, 1 or multiple R₈; Alternatively, R₁ and R₁₁ may be taken together to form a 3-6 membered saturated or partially saturated carbocycle or heterocycle, optionally substituted with 0, 1 or multiple R₈;

R₂ and R₁₂ are independently chosen from hydrogen or methyl;

R₃ is chosen from aryl or heteroaryl, each optionally substituted with 0, 1 or multiple R₈;

R₄ is chosen from alkyl, aryl, or acyl, each optionally substituted with 0, 1 or multiple R₈;

R₅ is chosen from alkoxy or benzyloxy, each optionally substituted with 0, 1, or multiple R₈;

R₆ is chosen from hydrogen, alkoxy, or halo, each optionally substituted with 0, 1, or multiple R₈;

R₇ is chosen from hydrogen, —C(O)R₉, or —CH₂OC(O)R₉;

R₈ is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkoxy, or heterocyclyl, each optionally substituted with 0, 1, or multiple R₁₀;

R₉ is chosen from alkyl, alkoxy, or aryl, each optionally substituted with 0, 1, or multiple R₈;

R₁₀ is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkoxy, or heterocyclyl.

Another embodiment of the present disclosure may include a fungicidal composition for the control or prevention of fungal attack comprising the compounds described above and a phytologically acceptable carrier material.

Yet another embodiment of the present disclosure may include a method for the control or prevention of fungal attack on a plant, the method including the steps of applying a fungicidally effective amount of one or more of the compounds described above to at least one of the fungus, the plant, and an area adjacent to the plant.

It will be understood by those skilled in the art that the following terms may include generic “R”-groups within their definitions, e.g., “the term alkoxy refers to an —OR substituent”. It is also understood that within the definitions for the following terms, these “R” groups are included for illustration purposes and should not be construed as limiting or being limited by substitutions about Formula I.

The term “alkyl” refers to a branched, unbranched, or saturated cyclic carbon chain, including, but not limited to, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tertiary butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

The term “alkenyl” refers to a branched, unbranched or cyclic carbon chain containing one or more double bonds including, but not limited to, ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like.

The terms “aryl” and “Ar” refer to any aromatic ring, mono- or bi-cyclic, containing 0 heteroatoms.

The term “heterocyclyl” refers to any aromatic or non-aromatic ring, mono- or bi-cyclic, containing one or more heteroatoms

The term “alkoxy” refers to an —OR substituent.

The term “hydroxyl” refers to a —OH substituent.

The term “amino” refers to an —N(R)₂ substituent.

The term “halogen” or “halo” refers to one or more halogen atoms, defined as F, Cl, Br, and I.

The term “nitro” refers to a —NO₂ substituent.

The term thioalkyl refers to a —SR substituent.

Throughout the disclosure, reference to the compounds of Formula I is read as also including all stereoisomers, for example diastereomers, enantiomers, and mixtures thereof. In another embodiment, Formula (I) is read as also including salts or hydrates thereof. Exemplary salts include, but are not limited to: hydrochloride, hydrobromide, hydroiodide, trifluoroacetate, and trifluoromethane sulfonate.

It is also understood by those skilled in the art that additional substitution is allowable, unless otherwise noted, as long as the rules of chemical bonding and strain energy are satisfied and the product still exhibits fungicidal activity.

Another embodiment of the present disclosure is a use of a compound of Formula I, for protection of a plant against attack by a phytopathogenic organism or the treatment of a plant infested by a phytopathogenic organism, comprising the application of a compound of Formula I, or a composition comprising the compound to soil, a plant, a part of a plant, foliage, and/or roots.

Additionally, another embodiment of the present disclosure is a composition useful for protecting a plant against attack by a phytopathogenic organism and/or treatment of a plant infested by a phytopathogenic organism comprising a compound of Formula I and a phytologically acceptable carrier material.

DETAILED DESCRIPTION

The compounds of the present disclosure may be applied by any of a variety of known techniques, either as the compounds or as formulations comprising the compounds. For example, the compounds may be applied to the roots or foliage of plants for the control of various fungi, without damaging the commercial value of the plants. The materials may be applied in the form of any of the generally used formulation types, for example, as solutions, dusts, wettable powders, flowable concentrate, or emulsifiable concentrates.

Preferably, the compounds of the present disclosure are applied in the form of a formulation, comprising one or more of the compounds of Formula I with a phytologically acceptable carrier. Concentrated formulations may be dispersed in water, or other liquids, for application, or formulations may be dust-like or granular, which may then be applied without further treatment. The formulations can be prepared according to procedures that are conventional in the agricultural chemical art.

The present disclosure contemplates all vehicles by which one or more of the compounds may be formulated for delivery and used as a fungicide. Typically, formulations are applied as aqueous suspensions or emulsions. Such suspensions or emulsions may be produced from water-soluble, water-suspendible, or emulsifiable formulations which are solids, usually known as wettable powders; or liquids, usually known as emulsifiable concentrates, aqueous suspensions, or suspension concentrates. As will be readily appreciated, any material to which these compounds may be added may be used, provided it yields the desired utility without significant interference with the activity of these compounds as antifungal agents.

Wettable powders, which may be compacted to form water-dispersible granules, comprise an intimate mixture of one or more of the compounds of Formula I, an inert carrier and surfactants. The concentration of the compound in the wettable powder may be from about 10 percent to about 90 percent by weight based on the total weight of the wettable powder, more preferably about 25 weight percent to about 75 weight percent. In the preparation of wettable powder formulations, the compounds may be compounded with any finely divided solid, such as prophyllite, talc, chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch, casein, gluten, montmorillonite clays, diatomaceous earths, purified silicates or the like. In such operations, the finely divided carrier and surfactants are typically blended with the compound(s) and milled.

Emulsifiable concentrates of the compounds of Formula I may comprise a convenient concentration, such as from about 1 weight percent to about 50 weight percent of the compound, in a suitable liquid, based on the total weight of the concentrate. The compounds may be dissolved in an inert carrier, which is either a water-miscible solvent or a mixture of water-immiscible organic solvents, and emulsifiers. The concentrates may be diluted with water and oil to form spray mixtures in the form of oil-in-water emulsions. Useful organic solvents include aromatics, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, for example, terpenic solvents, including rosin derivatives, aliphatic ketones, such as cyclohexanone, and complex alcohols, such as 2-ethoxyethanol.

Emulsifiers which may be advantageously employed herein may be readily determined by those skilled in the art and include various nonionic, anionic, cationic and amphoteric emulsifiers, or a blend of two or more emulsifiers. Examples of nonionic emulsifiers useful in preparing the emulsifiable concentrates include the polyalkylene glycol ethers and condensation products of alkyl and aryl phenols, aliphatic alcohols, aliphatic amines or fatty acids with ethylene oxide, propylene oxides such as the ethoxylated alkyl phenols and carboxylic esters solubilized with the polyol or polyoxyalkylene. Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts. Anionic emulsifiers include the oil-soluble salts (e.g., calcium) of alkylaryl sulphonic acids, oil-soluble salts or sulfated polyglycol ethers and appropriate salts of phosphated polyglycol ether.

Representative organic liquids which may be employed in preparing the emulsifiable concentrates of the compounds of the present disclosure are the aromatic liquids such as xylene, propyl benzene fractions; or mixed naphthalene fractions, mineral oils, substituted aromatic organic liquids such as dioctyl phthalate; kerosene; dialkyl amides of various fatty acids, particularly the dimethyl amides of fatty glycols and glycol derivatives such as the n-butyl ether, ethyl ether or methyl ether of diethylene glycol, the methyl ether of triethylene glycol, petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffinic oils, and the like; vegetable oils such as soy bean oil, rape seed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cotton seed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; esters of the above vegetable oils; and the like. Mixtures of two or more organic liquids may also be employed in the preparation of the emulsifiable concentrate. Organic liquids include xylene, and propyl benzene fractions, with xylene being most preferred in some cases. Surface-active dispersing agents are typically employed in liquid formulations and in an amount of from 0.1 to 20 percent by weight based on the combined weight of the dispersing agent with one or more of the compounds. The formulations can also contain other compatible additives, for example, plant growth regulators and other biologically active compounds used in agriculture.

Aqueous suspensions comprise suspensions of one or more water-insoluble compounds of Formula I, dispersed in an aqueous vehicle at a concentration in the range from about 1 to about 50 weight percent, based on the total weight of the aqueous suspension. Suspensions are prepared by finely grinding one or more of the compounds, and vigorously mixing the ground material into a vehicle comprised of water and surfactants chosen from the same types discussed above. Other components, such as inorganic salts and synthetic or natural gums, may also be added to increase the density and viscosity of the aqueous vehicle.

The compounds of Formula I can also be applied as granular formulations, which are particularly useful for applications to the soil. Granular formulations generally contain from about 0.5 to about 10 weight percent, based on the total weight of the granular formulation of the compound(s), dispersed in an inert carrier which consists entirely or in large part of coarsely divided inert material such as attapulgite, bentonite, diatomite, clay or a similar inexpensive substance. Such formulations are usually prepared by dissolving the compounds in a suitable solvent and applying it to a granular carrier which has been preformed to the appropriate particle size, in the range of from about 0.5 to about 3 mm. A suitable solvent is a solvent in which the compound is substantially or completely soluble. Such formulations may also be prepared by making a dough or paste of the carrier and the compound and solvent, and crushing and drying to obtain the desired granular particle.

Dusts containing the compounds of Formula I may be prepared by intimately mixing one or more of the compounds in powdered form with a suitable dusty agricultural carrier, such as, for example, kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1 to about 10 weight percent of the compounds, based on the total weight of the dust.

The formulations may additionally contain adjuvant surfactants to enhance deposition, wetting, and penetration of the compounds onto the target crop and organism. These adjuvant surfactants may optionally be employed as a component of the formulation or as a tank mix. The amount of adjuvant surfactant will typically vary from 0.01 to 1.0 percent by volume, based on a spray-volume of water, preferably 0.05 to 0.5 volume percent. Suitable adjuvant surfactants include, but are not limited to ethoxylated nonyl phenols, ethoxylated synthetic or natural alcohols, salts of the esters or sulphosuccinic acids, ethoxylated organosilicones, ethoxylated fatty amines, blends of surfactants with mineral or vegetable oils, crop oil concentrate (mineral oil (85%)+emulsifiers (15%)); nonylphenol ethoxylate; benzylcocoalkyldimethyl quaternary ammonium salt; blend of petroleum hydrocarbon, alkyl esters, organic acid, and anionic surfactant; C₉-C₁₁ alkylpolyglycoside; phosphated alcohol ethoxylate; natural primary alcohol (C₁₂-C₁₆) ethoxylate; di-sec-butylphenol EO-PO block copolymer; polysiloxane-methyl cap; nonylphenol ethoxylate+urea ammonium nitrrate; emulsified methylated seed oil; tridecyl alcohol (synthetic) ethoxylate (8EO); tallow amine ethoxylate (15 EO); PEG(400) dioleate-99. The formulations may also include oil-in-water emulsions such as those disclosed in U.S. patent application Ser. No. 11/495,228, the disclosure of which is expressly incorporated by reference herein.

The formulations may optionally include combinations that contain other pesticidal compounds. Such additional pesticidal compounds may be fungicides, insecticides, herbicides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds. Accordingly, in such embodiments, the other pesticidal compound is employed as a supplemental toxicant for the same or for a different pesticidal use. The compounds of Formula I and the pesticidal compound in the combination can generally be present in a weight ratio of from 1:100 to 100:1.

The compounds of the present disclosure may also be combined with other fungicides to form fungicidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure are often applied in conjunction with one or more other fungicides to control a wider variety of undesirable diseases. When used in conjunction with other fungicide(s), the presently claimed compounds may be formulated with the other fungicide(s), tank-mixed with the other fungicide(s) or applied sequentially with the other fungicide(s). Such other fungicides may include 2-(thiocyanatomethylthio)-benzothiazole, 2-phenylphenol, 8-hydroxyquinoline sulfate, ametoctradin, amisulbrom, antimycin, Ampelomyces quisqualis, azaconazole, azoxystrobin, Bacillus subtilis, Bacillus subtilis strain QST713, benalaxyl, benomyl, benthiavalicarb-isopropyl, benzovindiflupyr benzylaminobenzene-sulfonate (BABS) salt, bicarbonates, biphenyl, bismerthiazol, bitertanol, bixafen, blasticidin-S, borax, Bordeaux mixture, boscalid, bromuconazole, bupirimate, calcium polysulfide, captafol, captan, carbendazim, carboxin, carpropamid, carvone, chlazafenone, chloroneb, chlorothalonil, chlozolinate, Coniothyrium minitans, copper hydroxide, copper octanoate, copper oxychloride, copper sulfate, copper sulfate (tribasic), cuprous oxide, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dazomet, debacarb, diammonium ethylenebis-(dithiocarbamate), dichlofluanid, dichlorophen, diclocymet, diclomezine, dichloran, diethofencarb, difenoconazole, difenzoquat ion, diflumetorim, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap, diphenylamine, dithianon, dodemorph, dodemorph acetate, dodine, dodine free base, edifenphos, enestrobin, enestroburin, epoxiconazole, ethaboxam, ethoxyquin, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumorph, fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, guazatine, guazatine acetates, GY-81, hexachlorobenzene, hexaconazole, hymexazol, imazalil, imazalil sulfate, imibenconazole, iminoctadine, iminoctadine triacetate, iminoctadine tris(albesilate), iodocarb, ipconazole, ipfenpyrazolone, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isopyrazam, isotianil, kasugamycin, kasugamycin hydrochloride hydrate, kresoxim-methyl, laminarin, mancopper, mancozeb, mandipropamid, maneb, mefenoxam, mepanipyrim, mepronil, meptyl-dinocap, mercuric chloride, mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M, metam, metam-ammonium, metam-potassium, metam-sodium, metconazole, methasulfocarb, methyl iodide, methyl isothiocyanate, metiram, metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam, nitrothal-isopropyl, nuarimol, octhilinone, ofurace, oleic acid (fatty acids), orysastrobin, oxadixyl, oxine-copper, oxpoconazole fumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, pentachlorophenyl laurate, penthiopyrad, phenylmercury acetate, phosphonic acid, phthalide, picoxystrobin, polyoxin B, polyoxins, polyoxorim, potassium bicarbonate, potassium hydroxyquinoline sulfate, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyroquilon, quinoclamine, quinoxyfen, quintozene, Reynoutria sachalinensis extract, sedaxane, silthiofam, simeconazole, sodium 2-phenylphenoxide, sodium bicarbonate, sodium pentachlorophenoxide, spiroxamine, sulfur, SYP-Z048, tar oils, tebuconazole, tebufloquin, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin, valifenalate, valiphenal, vinclozolin, zineb, ziram, zoxamide, Candida oleophila, Fusarium oxysporum, Gliocladium spp., Phlebiopsis gigantea, Streptomyces griseoviridis, Trichoderma spp., (RS)—N-(3,5-dichlorophenyl)-2-(methoxymethyl)-succinimide, 1,2-dichloropropane, 1,3-dichloro-1,1,3,3-tetrafluoroacetone hydrate, 1-chloro-2,4-dinitronaphthalene, 1-chloro-2-nitropropane, 2-(2-heptadecyl-2-imidazolin-1-yl)ethanol, 2,3-dihydro-5-phenyl-1,4-dithi-ine 1,1,4,4-tetraoxide, 2-methoxyethylmercury acetate, 2-methoxyethylmercury chloride, 2-methoxyethylmercury silicate, 3-(4-chlorophenyl)-5-methylrhodanine, 4-(2-nitroprop-1-enyl)phenyl thiocyanateme, ampropylfos, anilazine, azithiram, barium polysulfide, Bayer 32394, benodanil, benquinox, bentaluron, benzamacril; benzamacril-isobutyl, benzamorf, binapacryl, bis(methylmercury) sulfate, bis(tributyltin) oxide, buthiobate, cadmium calcium copper zinc chromate sulfate, carbamorph, CECA, chlobenthiazone, chloraniformethan, chlorfenazole, chlorquinox, climbazole, copper bis(3-phenylsalicylate), copper zinc chromate, cufraneb, cupric hydrazinium sulfate, cuprobam, cyclafuramid, cypendazole, cyprofuram, decafentin, dichlone, dichlozoline, diclobutrazol, dimethirimol, dinocton, dinosulfon, dinoterbon, dipyrithione, ditalimfos, dodicin, drazoxolon, EBP, ESBP, etaconazole, etem, ethirim, fenaminosulf, fenapanil, fenitropan, fluotrimazole, furcarbanil, furconazole, furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin, halacrinate, Hercules 3944, hexylthiofos, ICIA0858, isopamphos, isovaledione, mebenil, mecarbinzid, metazoxolon, methfuroxam, methylmercury dicyandiamide, metsulfovax, milneb, mucochloric anhydride, myclozolin, N-3,5-dichlorophenyl-succinimide, N-3-nitrophenylitaconimide, natamycin, N-ethylmercurio-4-toluenesulfonanilide, nickel bis(dimethyldithiocarbamate), OCH, phenylmercury dimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, prothiocarb; prothiocarb hydrochloride, pyracarbolid, pyridinitril, pyroxychlor, pyroxyfur, quinacetol; quinacetol sulfate, quinazamid, quinconazole, rabenzazole, salicylanilide, SSF-109, sultropen, tecoram, thiadifluor, thicyofen, thiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos, triarimol, triazbutil, trichlamide, urbacid, zarilamid, and any combinations thereof.

Additionally, the compounds described herein may be combined with other pesticides, including insecticides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds to form pesticidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure may be applied in conjunction with one or more other pesticides to control a wider variety of undesirable pests. When used in conjunction with other pesticides, the presently claimed compounds may be formulated with the other pesticide(s), tank-mixed with the other pesticide(s) or applied sequentially with the other pesticide(s). Typical insecticides include, but are not limited to: 1,2-dichloropropane, abamectin, acephate, acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allyxycarb, alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan, amidithion, aminocarb, amiton, amiton oxalate, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, barium hexafluorosilicate, barthrin, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin, bioethanomethrin, biopermethrin, bistrifluron, borax, boric acid, bromfenvinfos, bromocyclen, bromo-DDT, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, calcium arsenate, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, cartap hydrochloride, chlorantraniliprole, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroform, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide, cinerin I, cinerin II, cinerins, cismethrin, cloethocarb, closantel, clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate, copper oleate, coumaphos, coumithoate, crotamiton, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, cyclethrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, cyromazine, cythioate, DDT, decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos, diatomaceous earth, diazinon, dicapthon, dichlofenthion, dichlorvos, dicresyl, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dilor, dimefluthrin, dimefox, dimetan, dimethoate, dimethrin, dimethylvinphos, dimetilan, dinex, dinex-diclexine, dinoprop, dinosam, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, d-limonene, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, doramectin, ecdysterone, emamectin, emamectin benzoate, EMPC, empenthrin, endosulfan, endothion, endrin, EPN, epofenonane, eprinomectin, esdepalléthrine, esfenvalerate, etaphos, ethiofencarb, ethion, ethiprole, ethoate-methyl, ethoprophos, ethyl formate, ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene oxide, etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazaflor, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion, fenthion-ethyl, fenvalerate, fipronil, flonicamid, flubendiamide, flucofuron, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flufenprox, fluvalinate, fonofos, formetanate, formetanate hydrochloride, formothion, formparanate, formparanate hydrochloride, fosmethilan, fospirate, fosthietan, furathiocarb, furethrin, gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD, heptachlor, heptenophos, heterophos, hexaflumuron, HHDN, hydramethylnon, hydrogen cyanide, hydroprene, hyquincarb, imidacloprid, imiprothrin, indoxacarb, iodomethane, IPSP, isazofos, isobenzan, isocarbophos, isodrin, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane, isothioate, isoxathion, ivermectin, jasmolin I, jasmolin II, jodfenphos, juvenile hormone I, juvenile hormone II, juvenile hormone III, kelevan, kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, leptophos, lindane, lirimfos, lufenuron, lythidathion, malathion, malonoben, mazidox, mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride, mesulfenfos, metaflumizone, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, methylchloroform, methylene chloride, metofluthrin, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, milbemycin oxime, mipafox, mirex, molosultap, monocrotophos, monomehypo, monosultap, morphothion, moxidectin, naftalofos, naled, naphthalene, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton, para-dichlorobenzene, parathion, parathion-methyl, penfluron, pentachlorophenol, permethrin, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phosphine, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassium arsenite, potassium thiocyanate, pp′-DDT, prallethrin, precocene I, precocene II, precocene III, primidophos, profenofos, profluralin, promacyl, promecarb, propaphos, propetamphos, propoxur, prothidathion, prothiofos, prothoate, protrifenbute, pyraclofos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins, pyridaben, pyridalyl, pyridaphenthion, pyrifluquinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxyfen, quassia, quinalphos, quinalphos-methyl, quinothion, rafoxanide, resmethrin, rotenone, ryania, sabadilla, schradan, selamectin, silafluofen, silica gel, sodium arsenite, sodium fluoride, sodium hexafluorosilicate, sodium thiocyanate, sophamide, spinetoram, spinosad, spiromesifen, spirotetramat, sulcofuron, sulcofuron-sodium, sulfluramid, sulfotep, sulfoxaflor, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachloroethane, tetrachlorvinphos, tetramethrin, tetramethylfluthrin, theta-cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon, thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triarathene, triazamate, triazophos, trichlorfon, trichlormetaphos-3, trichloronat, trifenofos, triflumuron, trimethacarb, triprene, vamidothion, vaniliprole, XMC, xylylcarb, zeta-cypermethrin, zolaprofos, and any combinations thereof.

Additionally, the compounds described herein may be combined with herbicides that are compatible with the compounds of the present disclosure in the medium selected for application, and not antagonistic to the activity of the present compounds to form pesticidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure may be applied in conjunction with one or more herbicides to control a wide variety of undesirable plants. When used in conjunction with herbicides, the presently claimed compounds may be formulated with the herbicide(s), tank-mixed with the herbicide(s) or applied sequentially with the herbicide(s). Typical herbicides include, but are not limited to: 4-CPA; 4-CPB; 4-CPP; 2,4-D; 3,4-DA; 2,4-DB; 3,4-DB; 2,4-DEB; 2,4-DEP; 3,4-DP; 2,3,6-TBA; 2,4,5-T; 2,4,5-TB; acetochlor, acifluorfen, aclonifen, acrolein, alachlor, allidochlor, alloxydim, allyl alcohol, alorac, ametridione, ametryn, amibuzin, amicarbazone, amidosulfuron, aminocyclopyrachlor, aminopyralid, amiprofos-methyl, amitrole, ammonium sulfamate, anilofos, anisuron, asulam, atraton, atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC, beflubutamid, benazolin, bencarbazone, benfluralin, benfuresate, bensulfuron, bensulide, bentazone, benzadox, benzfendizone, benzipram, benzobicyclon, benzofenap, benzofluor, benzoylprop, benzthiazuron, bicyclopyrone, bifenox, bilanafos, bispyribac, borax, bromacil, bromobonil, bromobutide, bromofenoxim, bromoxynil, brompyrazon, butachlor, butafenacil, butamifos, butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon, butylate, cacodylic acid, cafenstrole, calcium chlorate, calcium cyanamide, cambendichlor, carbasulam, carbetamide, carboxazole chlorprocarb, carfentrazone, CDEA, CEPC, chlomethoxyfen, chloramben, chloranocryl, chlorazifop, chlorazine, chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlornitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham, chlorsulfuron, chlorthal, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, cisanilide, clethodim, cliodinate, clodinafop, clofop, clomazone, clomeprop, cloprop, cloproxydim, clopyralid, cloransulam, CMA, copper sulfate, CPMF, CPPC, credazine, cresol, cumyluron, cyanatryn, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop, cyperquat, cyprazine, cyprazole, cypromid, daimuron, dalapon, dazomet, delachlor, desmedipham, desmetryn, di-allate, dicamba, dichlobenil, dichloralurea, dichlormate, dichlorprop, dichlorprop-P, diclofop, diclosulam, diethamquat, diethatyl, difenopenten, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimexano, dimidazon, dinitramine, dinofenate, dinoprop, dinosam, dinoseb, dinoterb, diphenamid, dipropetryn, diquat, disul, dithiopyr, diuron, DMPA, DNOC, DSMA, EBEP, eglinazine, endothal, epronaz, EPTC, erbon, esprocarb, ethalfluralin, ethametsulfuron, ethidimuron, ethiolate, ethofumesate, ethoxyfen, ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD, fenasulam, fenoprop, fenoxaprop, fenoxaprop-P, fenoxasulfone, fenteracol, fenthiaprop, fentrazamide, fenuron, ferrous sulfate, flamprop, flamprop-M, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr, flumetsulam, flumezin, flumiclorac, flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoromidine, fluoronitrofen, fluothiuron, flupoxam, flupropacil, flupropanate, flupyrsulfuron, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet, fomesafen, foramsulfuron, fosamine, furyloxyfen, glufosinate, glufosinate-P, glyphosate, halauxifen, halosafen, halosulfuron, haloxydine, haloxyfop, haloxyfop-P, hexachloroacetone, hexaflurate, hexazinone, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan, indaziflam, iodobonil, iodomethane, iodosulfuron, ioxynil, ipazine, ipfencarbazone, iprymidam, isocarbamid, isocil, isomethiozin, isonoruron, isopolinate, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate, ketospiradox, lactofen, lenacil, linuron, MAA, MAMA, MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, medinoterb, mefenacet, mefluidide, mesoprazine, mesosulfuron, mesotrione, metam, metamifop, metamitron, metazachlor, metazosulfuron, metflurazon, methabenzthiazuron, methalpropalin, methazole, methiobencarb, methiozolin, methiuron, methometon, methoprotryne, methyl bromide, methyl isothiocyanate, methyldymron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, molinate, monalide, monisouron, monochloroacetic acid, monolinuron, monuron, morfamquat, MSMA, naproanilide, napropamide, naptalam, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen, norflurazon, noruron, OCH, orbencarb, ortho-dichlorobenzene, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon, oxasulfuron, oxaziclomefone, oxyfluorfen, parafluron, paraquat, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentachlorophenol, pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham, phenmedipham-ethyl, phenobenzuron, phenylmercury acetate, picloram, picolinafen, pinoxaden, piperophos, potassium arsenite, potassium azide, potassium cyanate, pretilachlor, primisulfuron, procyazine, prodiamine, profluazol, profluralin, profoxydim, proglinazine, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron, propyzamide, prosulfalin, prosulfocarb, prosulfuron, proxan, prynachlor, pydanon, pyraclonil, pyraflufen, pyrasulfotole, pyrazolynate, pyrazosulfuron, pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate, pyriftalid, pyriminobac, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quinonamid, quizalofop, quizalofop-P, rhodethanil, rimsulfuron, saflufenacil, S-metolachlor, sebuthylazine, secbumeton, sethoxydim, siduron, simazine, simeton, simetryn, SMA, sodium arsenite, sodium azide, sodium chlorate, sulcotrione, sulfallate, sulfentrazone, sulfometuron, sulfosulfuron, sulfuric acid, sulglycapin, swep, TCA, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluron, thenylchlor, thiazafluron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone-methyl, thifensulfuron, thiobencarb, tiocarbazil, tioclorim, topramezone, tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam, tribenuron, tricamba, triclopyr, tridiphane, trietazine, trifloxysulfuron, trifluralin, triflusulfuron, trifop, trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron, vernolate, and xylachlor.

Another embodiment of the present disclosure is a method for the control or prevention of fungal attack. This method comprises applying to the soil, plant, roots, foliage, or locus of the fungus, or to a locus in which the infestation is to be prevented (for example applying to cereal or grape plants), a fungicidally effective amount of one or more of the compounds of Formula I. The compounds are suitable for treatment of various plants at fungicidal levels, while exhibiting low phytotoxicity. The compounds may be useful both in a protectant and/or an eradicant fashion.

The compounds have been found to have significant fungicidal effect particularly for agricultural use. Many of the compounds are particularly effective for use with agricultural crops and horticultural plants.

It will be understood by those skilled in the art that the efficacy of the compound for the foregoing fungi establishes the general utility of the compounds as fungicides.

The compounds have broad ranges of activity against fungal pathogens. Exemplary pathogens may include, but are not limited to, causing agent of wheat leaf blotch (Zymoseptoria tritici), wheat brown rust (Puccinia triticina), wheat stripe rust (Puccinia striiformis), scab of apple (Venturia inaequalis), powdery mildew of grapevine (Uncinula necator), barley scald (Rhynchosporium secalis), blast of rice (Pyricularia oryzae), rust of soybean (Phakopsora pachyrhizi), glume blotch of wheat (Leptosphaeria nodorum), powdery mildew of wheat (Blumeria graminis f. sp. tritici), powdery mildew of barley (Blumeria graminis f. sp. hordei), powdery mildew of cucurbits (Erysiphe cichoracearum), anthracnose of cucurbits (Colletotrichum lagenarium), leaf spot of beet (Cercospora beticola), early blight of tomato (Alternaria solani), and spot blotch of barley (Cochliobolus sativus). The exact amount of the active material to be applied is dependent not only on the specific active material being applied, but also on the particular action desired, the fungal species to be controlled, and the stage of growth thereof, as well as the part of the plant or other product to be contacted with the compound. Thus, all the compounds, and formulations containing the same, may not be equally effective at similar concentrations or against the same fungal species.

The compounds are effective in use with plants in a disease-inhibiting and phytologically acceptable amount. The term “disease-inhibiting and phytologically acceptable amount” refers to an amount of a compound that kills or inhibits the plant disease for which control is desired, but is not significantly toxic to the plant. This amount will generally be from about 0.1 to about 1000 ppm (parts per million), with 1 to 500 ppm being preferred. The exact concentration of compound required varies with the fungal disease to be controlled, the type of formulation employed, the method of application, the particular plant species, climate conditions, and the like. A suitable application rate is typically in the range from about 0.10 to about 4 pounds/acre (about 0.01 to 0.45 grams per square meter, g/m²).

Any range or desired value given herein may be extended or altered without losing the effects sought, as is apparent to the skilled person for an understanding of the teachings herein.

The compounds of Formula I may be made using well-known chemical procedures. Intermediates not specifically mentioned in this disclosure are either commercially available, may be made by routes disclosed in the chemical literature, or may be readily synthesized from commercial starting materials utilizing standard procedures.

General Schemes

The following schemes illustrate approaches to generating picolinamide compounds of Formula (I). The following descriptions and examples are provided for illustrative purposes and should not be construed as limiting in terms of substituents or substitution patterns.

Compounds of Formulae 1.1, 1.2, 1.3, and 1.4, wherein R₃ is as originally defined, can be prepared by the methods shown in Scheme 1, steps a-c. Compounds of Formula 1.0, wherein Z is ethoxy (—OCH₂CH₃, OEt) or pyrrolidine and P.G. is Bn or PMB, can be treated with a mixture of an organometallic nucleophile, such as phenylmagnesium bromide or phenyllithium, and a reducing agent, such as lithium borohydride (LiBH₄), in a polar, aprotic solvent such as tetrahydrofuran (THF) or diethyl ether (Et₂O) at a reduced temperature of about −78° C. to about 0° C. to afford compounds of Formula 1.1, wherein R₃ is as previously defined, as shown in step a. Alternatively, the compound of Formula 1.0, wherein Z is OEt and P.G. is Bn or PMB, can be converted to the aldehyde of Formula 1.2 by treating with a catalyst, such as chlorobis(cyclooctene)iridium(I) dimer (Ir₂(coe)₄Cl₂), and a reducing agent, such as diethylsilane (Et₂SiH₂), in a halogenated solvent such as dichloromethane (CH₂Cl₂), as described by Cheng, C.; Brookhart, M. Angew. Chem. Int. Ed. 2012, 51, 9422-9424 and shown in step b. Compounds of Formulas 1.3 and 1.4, wherein R₃ is as previously defined, can be obtained by treating the aldehyde of Formula 1.2 with a carbon nucleophile, such as phenyl magnesium bromide, in a polar aprotic solvent, such as THF, at a reduced temperature of about −78° C. to about 23° C., as depicted in step c.

Compounds of Formulas 2.1, 2.2 and 2.3, wherein R₃ is as originally defined, can be obtained using the methods outlined in Scheme 2, steps a-d. Compounds of Formula 2.1, wherein R₃ is as previously defined and R₄ is aryl, can be prepared by treating solutions of compounds of Formula 2.0, wherein R₃ is as originally defined, in a solvent such as toluene, with an organometallic species, such as bis(acetato-O)triphenyl-bismuth(V) (Ph₃Bi(OAc)₂), in the presence of a catalyst, such as copper(II) acetate (Cu(OAc)₂), at an elevated temperature of about 50° C., as shown in step a. Alternatively, arylated products of Formula 2.1, wherein R₃ is as previously defined, can be prepared by treating compounds of Formula 2.0, wherein R₃ is as previously defined, with an aryl fluoride, such as 1,3-difluorobenzene, and an alkoxide base, such as potassium tert-butoxide (KOt-Bu) or sodium hydride (NaH), in a polar aprotic solvent, such as N,N-dimethyl formamide (DMF) or dimethyl sulfoxide (DMSO), at an elevated temperature of about 50° C. to about 70° C., as shown in step b. Compounds of Formula 2.2, wherein R₃ is as previously defined and R₄ is alkyl, can be prepared from compounds of Formula 2.0, wherein R₃ is as previously defined, by treating with a base, such as KOt-Bu or NaH, and an electrophile, such as an alkyl halide such as (bromomethyl)cyclopropane, in a polar aprotic solvent such as DMF, at an elevated temperature of about 50° C., as shown in step c. Compounds of Formula 2.3, wherein R₃ is as previously defined and R₄ is acyl, can be prepared from compounds of Formula 2.0, by treating with an acyl electrophile, such as an acyl chloride, in a pyridine solvent at ambient temperature as shown in step d.

Compounds of Formula 3.2, wherein R₄ and R₈ are as originally defined, can be prepared according to the methods outlined in Scheme 3, steps a-c. Compounds of Formula 3.0, wherein R₄ is as originally defined, can be subjected to a palladium catalyst, such as tetrakis(triphenylphosphine)palladium(0) (Pd(PPh₃)₄), and a secondary amine, such as morpholine, in a polar aprotic solvent, such as THF, at a temperature of about 23° C. to afford compounds of Formula 3.1, wherein R₄ is as originally defined, as shown in step a. Compounds of Formula 3.2, wherein R₄ is as originally defined and R₈ is alkyl, can be prepared from compounds of Formula 3.1, wherein R₄ is as originally defined, by treatment with a base, such as potassium carbonate (K₂CO₃), and an alkyl bromide, such as (bromomethyl)cyclohexane, in a polar aprotic solvent, such as acetone, at a temperature of about 25° C. to about 50° C., as shown in step b. Additionally, compounds of Formula 3.2, wherein R₄ is as originally defined and R₈ is aryl, can be prepared from alcohols of Formula 3.1, wherein R₄ is as previously defined, by treatment with a copper catalyst, such as Cu(OAc)₂, an aryl boronic acid, such as phenyl boronic acid, and a tertiary amine, such as triethylamine (NEt₃), in a halogenated solvent, such as CH₂Cl₂, in the presence of 4 Å molecular sieves at a temperature of approximately 23° C., as described by Nie, Z.; Perretta, C.; Lu, J.; Su, Y.; Margosiak, S.; Gajiwala, K. S.; Cortez, J.; Nikulin, V.; Yager, K. M.; Appelt, K.; Chu, S. J. Med. Chem., 2005, 48 (5), pp 1596-1609, and shown in step c.

Compounds of Formula 4.2, wherein R₃ and R₄ are as originally defined, can be prepared according to the methods outlined in Scheme 4, steps a-c. Compounds of Formula 4.2, wherein R₃ and R₄ are as previously defined but not alkenyl, can be prepared by treating compounds of Formula 4.0, wherein R₃ and R₄ are originally defined, with a catalyst, such as palladium on carbon (Pd/C), in the presence of hydrogen gas (H₂) in a polar solvent, such as ethyl acetate (EtOAc) or MeOH, or with an alternate source of hydrogen, such as cyclohexene, in a polar solvent such as EtOH, as shown in step a. Additionally, compounds of Formula 4.0, wherein R₃ is as previously defined and R₄ is an aryl chloride, can be subjected to modified hydrogenolysis conditions, by exposing an EtOH solution of the aryl chloride to H₂ in the presence of Pd/C and NEt₃ to afford compounds of Formula 4.2, wherein R₃ and R₄ are as originally defined, but not alkenyl or chloro, as shown in step b. Compounds of Formula 4.2, wherein R₃ and R₄ are as originally defined, can be obtained by treating compounds of Formula 4.1, wherein R₃ and R₄ are as originally defined, with an oxidant, such as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), in a solvent mixture, such as aqueous CH₂Cl₂, as indicated in step c.

Compounds of Formula 5.2, wherein R₁, R₂, R₃, R₄, R₁₁, and R₁₂, are as originally defined, can be prepared according to the method outlined in Scheme 5, step a. Alcohols of Formula 5.0, wherein R₂, R₃, R₄, and R₁₂, are as originally defined, can be treated with compounds of Formula 5.1, wherein R₁ and R₁₁ are as originally defined, a coupling reagent, such as 3-(ethyliminomethyleneamino)-N,N-dimethylpropan-1-amine hydrochloride (EDC) or a polymer-supported carbodiimide (PS-CDT), and a catalyst, such as N,N-dimethylpyridin-4-amine (DMAP), in a halogenated solvent, such as CH₂Cl₂, to afford compounds of Formula 5.2, wherein R₁, R₂, R₃, R₄, R₁₁, and R₁₂ are as previously defined, as shown in step a.

Compounds of Formula 6.4, wherein R₁, R₂, R₃, R₄, R₆, R₁₁, and R₁₂ are as originally defined, can be prepared according to the methods outlined in Scheme 6, steps a-d. Compounds of Formula 6.0, wherein R₁, R₂, R₃, R₄, R₁₁, and R₁₂ are as originally defined, but not alkenyl, can be treated with an acid, such as a 4 N solution of HCl in dioxane, in a halogenated solvent such as CH₂Cl₂ to afford compounds of Formula 6.1, wherein R₁, R₂, R₃, R₄, R₁₁, and R₁₂, are as originally defined, but not alkenyl, as shown in step a. Compounds of Formula 6.2, wherein R₁, R₂, R₃, R₄, R₁₁, and R₁₂ are as originally defined, can be prepared by treating compounds of Formula 6.0, wherein R₁, R₂, R₃, R₄, R₁₁, and R₁₂ are as originally defined, with an acid, such as 2,2,2-trifluoroacetic acid, in a halogenated solvent such as CH₂Cl₂, as shown in step b. Compounds of Formulas 6.1 and 6.2, wherein R₁, R₂, R₃, R₄, R₁₁, and R₁₂ are as originally defined, can be treated with compounds of Formula 6.3, wherein R₆ is as originally defined, in the presence of a base, such as diisopropylethylamine, and a peptide coupling reagent, such as benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate (PyBOP) or O-(7-azabenzo-triazol-1-yl)-N,N,N′,N′-tetramethyluronium hexafluorophosphate (HATU), in an halogenated solvent such as CH₂Cl₂, to afford compounds of Formula 6.4, wherein R₁, R₂, R₃, R₄, R₆, R₁₁, and R₁₂ are as previously defined, as shown in step c.

Compounds of Formula 7.1, wherein R₁, R₂, R₃, R₆, R₁₁, and R₁₂ are as originally defined, but not alkenyl, and R₈ is as originally defined, but not alkenyl or chloro, can be prepared according to the method outlined in Scheme 7, step a. Compounds of Formula 7.0, wherein R₁, R₂, R₃, R₆, R₈, R₁₁, and R₁₂ are as originally defined, can be subjected to the hydrogenation conditions described in Scheme 4, step b to afford compounds of Formula 7.1, wherein R₁, R₂, R₃, R₆, R₈, R₁₁, and R₁₂ are as previously defined, as depicted in step a.

Compounds of Formula 8.1, wherein R₁, R₂, R₃, R₄, R₆, R₇, R₁₁, and R₁₂ are as originally defined, can be prepared according to the method outlined in Scheme 8, steps a or b. Compounds of Formula 8.0, wherein R₁, R₂, R₃, R₄, R₆, R₁₁, and R₁₂ are as previously defined, can be treated with an appropriate alkyl halide with or without a reagent such as sodium iodide (NaI) and an alkali carbonate base, such as Na₂CO₃ or potassium carbonate (K₂CO₃), in a solvent such as acetone, as shown in step a. Or, alternatively, by treatment with an acyl halide or anhydride in the presence of an amine base, such as pyridine, NEt₃, DMAP, or mixtures thereof, in an aprotic solvent, such as CH₂Cl₂, to afford compounds of Formula 8.1, wherein R₁, R₂, R₃, R₄, R₆, R₇, R₁₁, and R₁₂ are as previously defined, as shown in step b.

Compounds of Formula 9.1 and 9.2, wherein R₁, R₂, R₄, R₆, R₁₁, and R₁₂ are as originally defined, but not alkenyl, and R₈ is as originally defined, but not allyloxy or alkenyl, can be prepared according to the method outlined in Scheme 9, step a. Compounds of Formula 9.0, wherein R₁, R₂, R₄, R₆, R₈, R₁₁, and R₁₂ are as originally defined, can be treated with a ruthenium catalyst, such as ruthenium trichloride n-hydrate, and a hydride source, such as sodium borohydride (NaBH₄), in a polar aprotic solvent, such as THF, in the presence of water, at a temperature of about 0° C. to afford compounds of Formula 9.1 and 9.2, as described by Sharma, P. K.; Kumar, S.; Kumar, P.; Nielson, P. Tet. Lett. 2012, 48, 8704-8708 and shown in step a.

Compounds of Formula 10.3, wherein R₂, R₃, R₄ and R₁₂ are as originally defined, can be prepared according to the methods outlined in Scheme 10, steps a-c. Compounds of Formula 10.0, wherein R₃ is as originally defined, can be transformed into a Grignard reagent by being subjected to magnesium metal in the presence of a lithium salt, such as lithium chloride (LiCl) in a polar aprotic solvent, such as THF, at an elevated temperature of about 70° C. The subsequent Grignard reagent can then be subjected to an iron catalyst, such as tris(acetylacetonato) iron(III) (Fe(acac)₃), and an alkyl chloride, such as allyl chloride, in a polar aprotic solvent, such as THF, at an elevated temperature of about 70° C. to afford compounds of Formula 10.1, wherein R₂, R₃, R₁₂ are as originally defined, as described by Mayer, M.; Welther, A.; von Wangelin, A. J. Chem Cat Chem, 2011, 3, pp 1567-1571, and as shown in step a. Compounds of Formula 10.2, wherein R₂, R₃, and R₁₂ are as originally defined, can be prepared from compounds of Formula 10.1, wherein R₂, R₃, and R₁₂ are as originally defined, by treatment with an ammonium salt such as tetra n-butylammonium hydrogen sulfate, an epoxidation catalyst, such as 1,2:4,5-Bis-O-(isopropylidene)-β-L-erythro-2,3-hexodiulo-2,6-pyranose (Shi epoxidation catalyst enantiomer), a buffer solution, such as 0.05 M Na₂B₄O₇-10H₂O in 4×10⁻⁴ M aqueous Na₂(EDTA), in a polar aprotic solvent, such as acetonitrile, at a temperature of about 0° C. Followed by slow addition of an oxidant such as Oxone in a solution of Na₂(EDTA) and simultaneous slow addition of a solution of a base such as K₂CO₃ in water as described by Wang, Z.-X.; Tu, Y.; Frohn, M.; Zhang, J.-R.; Shi, Y. J. Am. Chem. Soc, 1997, 119, pp 11224-11235, and as shown in step b. Additionally, compounds of Formula 10.3, wherein R₂, R₃, R₄ and R₁₂ are as originally defined, can be prepared from epoxides of Formula 10.2, wherein R₂, R₃, R₁₂ are as previously defined, by treatment with an acid, such as sulfuric acid (H₂SO₄) in a mixture of an alcohol substituted with R₄ wherein R₄ is as previously defined, such as cyclopropanol, at a reduced temperature of about 0° C., as described by Aggarwal, V. K; Bae, I; Lee, H.-Y. Tetrahedron, 2006, 60 (43), pp 9725-9733, and shown in step c.

EXAMPLES Example 1A: Preparation of (1R,2S)-1-(4-fluorophenyl)-2-((4-methoxybenzyl)oxy)propan-1-ol

To a solution of (4-fluorophenyl)magnesium bromide (7.08 mL, 5.67 mmol) and lithium borohydride (LiBH₄) (2.83 mL, 5.67 mmol, 2.0 molar (M) in THF) in anhydrous Et₂O (11.45 mL) at −15° C. was added (S)-ethyl 2-((4-methoxybenzyl)oxy)propanoate (1.35 g, 5.67 mmol) as a 1M solution in anhydrous Et₂O (5.67 mL) via addition funnel over approximately a 40 minute (min) period at a rate that maintained an internal temperature between −7 and −15° C. The reaction vessel was allowed to slowly warm to room temperature (rt) overnight. The reaction mixture was cooled to 0° C. and quenched via slow addition of saturated aqueous ammonium chloride (NH₄Cl, 25 mL) followed by water (H₂O, 25 mL). The mixture was transferred to a separatory funel, and the aqueous (aq.) phase was extracted with Et₂O (3×50 mL). The combined organic phases were dried over magnesium sulfate (MgSO₄), filtered, and concentrated. The resulting residue was purified by flash column chromatography (silica gel (SiO₂), 5→25% acetone in hexanes) to afford the title compound (214 mg, 13%) as a colorless oil: ¹H NMR (400 MHz, CDCl₃) δ 7.33-7.27 (m, 2H), 7.25-7.21 (m, 2H), 7.05-6.98 (m, 2H), 6.91-6.86 (m, 2H), 4.85 (t, J=3.3 Hz, 1H), 4.57 (d, J=11.4 Hz, 1H), 4.46 (d, J=11.4 Hz, 1H), 3.81 (s, 3H), 3.69 (qd, J=6.3, 4.0 Hz, 1H), 2.53 (d, J=2.9 Hz, 1H), 1.02 (d, J=6.3 Hz, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ −115.49 (s); ESIMS m/z 603 ([2M+Na]⁺).

Example 1B: Preparation of (S)-2-((4-methoxybenzyl)oxy)propanal

To a solution of (S)-ethyl 2-((4-methoxybenzyl)oxy)propanoate (5.00 g, 21.0 mmol) in CH₂Cl₂ (30 mL) at 0° C. was added chlorobis(cyclooctene)iridium(I) dimer (Ir₂Cl₂(coe)₄); 94.0 milligrams (mg), 0.105 mmol) followed by diethylsilane (Et₂SiH₂; 4.08 mL, 31.5 mmol) over 10 min. The mixture was stirred at 0° C. for 30 min, then was warmed to rt and stirred for 3 h. The reaction mixture was cooled to 0° C. and quenched by adding 1 normal (N) aq. hydrogen chloride (HCl; 12 mL). The resulting solution was warmed to rt and stirred for 15 min. The phases were separated, and the aq. phase was extracted with CH₂Cl₂ (3×30 mL). The combined organic phases were washed with brine, dried over sodium sulfate (Na₂SO₄), filtered, evaporated, and purified by flash column chromatography (SiO₂, 2→50% acetone in hexanes) to afford the title compound (4.27 g, 100%) as a yellow oil: IR (Thin Film) 2934, 2837, 2865, 1731, 1512 cm⁻¹; ¹H NMR (300 MHz, CDCl₃) δ 9.64 (d, J=1.9 Hz, 1H), 7.35-7.21 (m, 2H), 6.95-6.79 (m, 2H), 4.63-4.40 (m, 2H), 3.94-3.76 (m, 1H), 3.81 (s, 3H), 1.31 (d, J=6.9 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 203.58, 159.54, 129.65, 129.37, 113.98, 79.14, 71.75, 55.30, 15.34.

Example 1C: Preparation of (1S,2S)-2-((4-methoxybenzyl)oxy)-1-phenylpropan-1-ol

To a solution of (S)-2-((4-methoxybenzyl)oxy)propanal (3.38 g, 17.4 mmol) in Et₂O (58 mL) at −78° C. was added phenylmagnesium bromide (34.8 mL, 34.8 mmol, 1 M in THF) dropwise. The reaction mixture was stirred and allowed to warm to rt overnight. The reaction was quenched by addition of sat. aq. ammonium chloride (NH₄Cl). The mixture was partitioned between H₂O and EtOAc, the phases were separated, and the aqueous phase was extracted with EtOAc (2×). The combined organic phases were washed with brine, dried over Na₂SO₄, filtered and concentrated. Purification via flash column chromatography (SiO₂, 2→50% acetone in hexanes) afforded an inseparable mixture of diastereomers (d.r. 3:1 SS:RS) of the title compound (3.29 g, 66%) as a yellow oil: ¹H NMR (400 MHz, CDCl₃; major) δ 7.37-7.25 (m, 7H), 6.89 (d, J=8.6 Hz, 2H), 4.62 (d, J=11.0 Hz, 1H), 4.44 (dd, J=7.8, 2.1 Hz, 1H), 4.41 (d, J=11.0 Hz, 1H), 3.82 (s, 3H), 3.60 (dq, J=7.8, 6.2 Hz, 1H), 3.21 (d, J=2.1 Hz, 1H), 1.05 (d, J=6.2 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 159.34, 140.56, 130.21, 129.46, 128.31, 127.25, 126.31, 113.93, 79.66, 78.32, 70.92, 55.30, 15.56; ESIMS m/z 295 ([M+Na]⁺).

Example 1D: Preparation of (1S,2S)-2-((4-methoxybenzyl)oxy)-1-(thiophen-2-yl)propan-1-ol and (1R,2S)-2-((4-methoxybenzyl)oxy)-1-(thiophen-2-yl)propan-1-ol

To a solution of thiophen-2-yllithium (4.00 mL, 4.00 mmol, 1 M in THF) and lithium borohydride (LiBH₄; 1.30 mL, 2.60 mmol, 2 M in THF) in THF (10 mL) at −10° C. was added neat (S)-2-((4-methoxybenzyl)oxy)-1-(pyrrolidin-1-yl)propan-1-one (0.527 g, 2.00 mmol) (for preparation see: Pellicena, M.; Solsona, J. G.; Romea, P.; Urpi, F. Tetrahedron 2012, 68, 10338.) dropwise via syringe pump addition over approximately a 1 h period, at a rate which maintained the internal temperature below −5° C. The reaction vessel was allowed to slowly warm to rt overnight. The reaction mixture was quenched by addition of sat. aq. NH₄Cl. The aqueous phase was extracted with Et₂O (3×). The combined organic phases were washed with brine, dried over Na₂SO₄, filtered, and concentrated. Purification via flash column chromatography (SiO₂, 2→10% acetone in hexanes) afforded the title compounds (0.231 g, 41% and 0.175 g, 31%, respectively) as colorless oils: major: ¹H NMR (300 MHz, CDCl₃) δ 7.32-7.21 (m, 3H), 7.05-6.93 (m, 2H), 6.94-6.83 (m, 2H), 5.03 (t, J=4.2 Hz, 1H), 4.61 (d, J=11.4 Hz, 1H), 4.48 (d, J=11.3 Hz, 1H), 3.81 (s, 3H), 3.88-3.73 (m, 1H), 2.59 (d, J=4.4 Hz, 1H), 1.13 (d, J=6.3 Hz, 3H); ESIMS m/z 579 ([2M+Na]⁺); minor: ¹H NMR (300 MHz, CDCl₃) δ 7.34-7.22 (m, 3H), 7.06-6.92 (m, 2H), 6.95-6.84 (m, 2H), 4.73 (dd, J=7.3, 2.7 Hz, 1H), 4.63 (d, J=10.9 Hz, 1H), 4.44 (d, J=11.0 Hz, 1H), 3.82 (s, 3H), 3.67 (dq, J=7.3, 6.2 Hz, 1H), 3.29 (d, J=2.8 Hz, 1H), 1.14 (d, J=6.1 Hz, 3H); ESIMS m/z 579 ([2M+Na]⁺).

Example 1E: Preparation of (1R,2S)-1-(4-fluoro-2-methoxyphenyl)-2-((4-methoxybenzyl)oxy)propan-1-ol

To a reaction flask was added 1-bromo-4-fluoro-2-methoxybenzene (0.4 g, 1.951 mmol) and dry diethyl ether (9.75 ml). The flask was sealed, evacuated and backfilled with nitrogen, and cooled to −78° C. Then, n-BuLi (2.5 M in hexanes, 0.780 ml, 1.951 mmol) was added to the reaction, and the reaction mixture was stirred at −78° C. for 1 h. LiBH₄ (2.0M in THF, 0.975 ml, 1.951 mmol) was added, followed by dropwise addition of (9-ethyl 2-((4-methoxybenzyl)oxy)propanoate (0.465 g, 1.951 mmol) as a 0.5 M solution in dry diethyl ether. The reaction was allowed to gradually warm to rt as the cooling bath expired overnight. The reaction was quenched by careful addition of 2 mL sat. aq. NH₄Cl (gas evolution noted), and allowed to stir for 30 min. At this point the mixture was transferred to a separatory funnel containing water and extracted 3× with diethyl ether. The combined organic layers were dried over MgSO₄, filtered and concentrated in vacuo. The resulting residue was purified via flash chromatography (SiO₂, 5→30% acetone in hexanes) to afford the title compound (290 mg, 46%) as a colorless oil. ¹H NMR (300 MHz, CDCl₃) δ 7.42 (dd, J=8.1, 7.2 Hz, 1H), 7.27-7.21 (m, 2H), 6.91-6.85 (m, 2H), 6.66 (td, J=8.4, 2.4 Hz, 1H), 6.55 (dd, J=10.9, 2.4 Hz, 1H), 5.15 (t, J=3.5 Hz, 1H), 4.57 (d, J=11.6 Hz, 1H), 4.50 (d, J=11.6 Hz, 1H), 3.86-3.78 (m, 4H), 3.76 (s, 3H), 2.65 (dd, J=3.4, 2.0 Hz, 1H), 1.00 (d, J=6.4 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 162.88 (d, J=244.4 Hz), 159.19, 157.03 (d, J=9.6 Hz), 130.66, 129.30, 128.47 (d, J=9.9 Hz), 124.48 (d, J=3.2 Hz), 113.76, 106.79 (d, J=20.9 Hz), 98.43 (d, J=25.9 Hz), 75.79 (d), 70.35, 69.97, 55.45, 55.30, 13.46; ESIMS m/z 663 ([2M+Na]⁺).

Example 2A: Preparation of 1-methoxy-2-((1R,2S)-2-((4-methoxybenzyl)oxy)-1-phenoxypropyl)benzene

To a solution of (1R,2S)-2-((4-methoxybenzyl)oxy)-1-(2-methoxyphenyl)propan-1-ol (500 mg, 1.654 mmol), N-cyclohexyl-N-methylcyclohexanamine (531 μl, 2.480 mmol) and Cu(OAc)₂ (60.1 mg, 0.331 mmol) in toluene (8.267 mL) was added Ph₃Bi(OAc)₂ (1385 mg, 2.480 mmol). The resulting blue suspension was heated to and stirred at 50° C. for 16 h. The reaction was cooled to rt, filtered through a plug of Celite™, and concentrated. The resulting crude material was purified via flash column chromatography (SiO₂, 0→30% acetone in hexanes) to give the title compound (555 mg, 67%) as a yellow oil: ¹H NMR (300 MHz, CDCl₃) δ 7.41-7.33 (m, 3H), 7.18 (q, J=8.2 Hz, 5H), 7.08 (d, J=8.0 Hz, 1H), 6.89-6.81 (m, 7H), 5.73 (d, J=3.5 Hz, 1H), 4.60-4.49 (m, 2H), 3.88-3.82 (m, 4H), 3.79 (s, 3H), 1.25 (d, J=6.4 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 158.98, 158.27, 156.42, 129.42, 129.18, 128.47, 127.69, 125.82, 121.56, 120.76, 120.46, 115.71, 113.59, 110.12, 76.32, 75.29, 70.61, 55.38, 55.27, 14.75; ESIMS m/z 779 ([2M+Na]⁺).

Example 2B: Preparation of 2-chloro-1-((1R,2S)-1-(4-fluoro-2-methoxyphenyl)-2-((4-methoxybenzyl)oxy)propoxy)-4-methylbenzene

To a solution of (1R,2S)-1-(4-fluoro-2-methoxyphenyl)-2-((4-methoxybenzyl)oxy)propan-1-ol (190 mg, 0.593 mmol) in anhydrous DMSO (2.97 mL) was added NaH (29.7 mg, 0.741 mmol, 60 wt % in mineral oil). After stirring for 10 min, 2-chloro-1-fluoro-4-methylbenzene (686 mg, 4.74 mmol) was added, and the reaction mixture was heated to 60° C. for 15 h. The reaction was quenched by slow addition of H₂O. The mixture was extracted Et₂O (3×50 mL) and the combined organic layers were dried by passing through a phase separator. Volatiles were removed under a gentle stream of N₂ and the resulting residue was purified via flash column chromatography (SiO₂, 0→30% acetone in hexanes) to afford the title compound (217 mg, 82%) as a colorless oil: ¹HNMR (400 MHz, CDCl₃) δ 7.34 (dd, J=9.2, 6.8 Hz, 1H), 7.19 (d, J=8.7 Hz, 2H), 7.14 (d, J=1.7 Hz, 1H), 6.85-6.77 (m, 3H), 6.62-6.55 (m, 3H), 5.63 (d, J=3.8 Hz, 1H), 4.63 (d, J=11.9 Hz, 1H), 4.57 (d, J=11.9 Hz, 1H), 3.89 (qd, J=6.4, 3.9 Hz, 1H), 3.83 (s, 3H), 3.79 (s, 3H), 2.19 (s, 3H), 1.25 (d, J=6.4 Hz, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ −112.06 (s); ESIMS m/z 467 ([M+Na]⁺).

Example 2C: Preparation of 4-((1R,2S)-2-(benzyloxy)-1-(cyclopropylmethoxy)-propyl)-1,1′-biphenyl

To a solution of (1R,2S)-1-([1,1′-biphenyl]-4-yl)-2-(benzyloxy)propan-1-ol (272 mg, 0.854 mmol) in anhydrous DMF (2.8 mL) at 0° C. was added sodium hydride (NaH; 59.8 mg, 1.50 mmol, 60 wt % in mineral oil). The reaction mixture was stirred at 0° C. for 15 min. The mixture was removed from the ice bath, was stirred for 15 min, and then was recooled back to 0° C. The reaction was treated with (bromomethyl)cyclopropane (84 μL, 0.854 mmol) and was allowed to stir at 0° C. After 10 min, the reaction vessel was removed from the ice bath and the reaction mixture was allowed to stir and warm to rt overnight. The reaction mixture was carefully quenched by the addition of H₂O. The crude reaction mixture was stirred for 10 min, and the phases were separated. The aq. phase was extracted with Et₂O (3×), and the combined organic phases were dried over Na₂SO₄, filtered, and concentrated. The resulting oil was purified by flash column chromatography (SiO₂, 0→10% acetone in hexanes) to afford the title compound (251 mg, 79%) as a colorless oil: ¹H NMR (400 MHz, CDCl₃) δ 7.64-7.60 (m, 2H), 7.57 (d, J=8.2 Hz, 2H), 7.48-7.32 (m, 5H), 7.24-7.19 (m, 3H), 7.10-7.06 (m, 2H), 4.46 (d, J=11.9 Hz, 1H), 4.30 (d, J=11.9 Hz, 1H), 4.27 (d, J=6.4 Hz, 1H), 3.64 (p, J=6.2 Hz, 1H), 3.28-3.20 (m, 2H), 1.32 (d, J=6.2 Hz, 3H), 1.12-1.01 (m, 1H), 0.56-0.45 (m, 2H), 0.22-0.10 (m, 2H); ¹³C NMR (101 MHz, CDCl3) δ 141.03, 140.33, 139.54, 138.60, 128.75, 128.18, 128.14, 127.67, 127.30, 127.18, 127.06, 126.73, 84.36, 78.56, 73.75, 71.47, 16.71, 10.74, 3.18, 2.83; ESIMS m/z 395 ([M+Na]⁺).

Example 2D: Preparation (1R,2S)-1-(4-fluoro-2-methoxyphenyl)-2-((4-methoxybenzyl)oxy)propyl pivalate

To a solution of (1R,2S)-1-(4-fluoro-2-methoxyphenyl)-2-((4-methoxybenzyl)oxy)propan-1-ol (85 mg, 0.265 mmol)) in anhydrous pyridine (0.858 mL) at 25° C. was added pivaloyl chloride (65.3 μL, 0.531 mmol). The reaction mixture was stirred at 25° C. for 16 h. The reaction was diluted with toluene and volatiles were removed by rotary evaporation. The resulting oil was purified by flash column chromatography (SiO₂, 5→30% acetone in hexanes) to afford the title compound (91 mg, 85%) as a colorless oil: ¹H NMR (300 MHz, CDCl₃) δ 7.22 (dt, J=5.8, 2.9 Hz, 3H), 6.88-6.82 (m, 2H), 6.67-6.54 (m, 2H), 6.39 (d, J=3.3 Hz, 1H), 4.60 (d, J=11.6 Hz, 1H), 4.49 (d, J=11.6 Hz, 1H), 3.83-3.74 (m, 7H), 1.26 (s, 9H), 1.10 (d, J=6.5 Hz, 3H); ¹⁹F NMR (471 MHz, CDCl₃) δ −112.37-−112.55 (m); ESIMS m/z 427 ([M+Na]⁺).

Example 3A: Preparation of 5-fluoro-2-((1R,2S)-2-((4-methoxybenzyl)oxy)-1-phenoxypropyl)phenol

To solution of 2-(allyloxy)-4-fluoro-1-((1R,2S)-2-((4-methoxybenzyl)oxy)-1-phenoxypropyl)benzene (294 mg, 0.696 mmol) and morpholine (72.8 μL, 0.835 mmol) in anhydrous THF (3.48 mL) was added Pd(PPh₃)₄ (40.2 mg, 0.035 mmol). The mixture was stirred at 25° C. for 5 h, and then was quenched by the addition of water. The mixture was diluted with Et₂O, transferred to a separatory funnel and washed with 1N HCl (3×50 mL). The organic layer was dried by passing through a phase separator, and the volatiles were removed in vacuo. The resulting residue was purified by flash column chromatography (SiO₂, 5→15% acetone in hexanes) to afford the title compound (228 mg, 86%) as a viscous oil: ¹H NMR (400 MHz, CDCl₃) δ 8.01 (s, 1H), 7.18 (ddt, J=9.8, 4.7, 2.4 Hz, 4H), 7.07 (dd, J=8.5, 6.6 Hz, 1H), 6.91 (t, J=7.4 Hz, 1H), 6.86-6.79 (m, 4H), 6.61 (dd, J=10.3, 2.5 Hz, 1H), 6.54 (td, J=8.3, 2.6 Hz, 1H), 5.01 (d, J=6.3 Hz, 1H), 4.60 (d, J=11.2 Hz, 1H), 4.43 (d, J=11.2 Hz, 1H), 4.03 (p, J=6.2 Hz, 1H), 3.80 (s, 3H), 1.30 (d, J=6.2 Hz, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ −112.86 (s); ESIMS m/z 381 ([M−H]⁻).

Example 3B: Preparation of 2-(cyclopropylmethoxy)-4-fluoro-1-((1R,2S)-2-((4-methoxybenzyl)oxy)-1-phenoxypropyl)benzene

To a mixture of 5-fluoro-2-((1R,2S)-2-((4-methoxybenzyl)oxy)-1-phenoxypropyl)phenol (114 mg, 0.298 mmol), and K₂CO₃ (82 mg, 0.596 mmol) in acetone (1.49 mL) was added (bromomethyl)cyclopropane (43.4 μL, 0.447 mmol). The reaction mixture was stirred at 25° C. for 24 h. Potassium carbonate (82 mg, 0.596 mmol) and (bromomethyl)cyclopropane (43.4 μL, 0.447 mmol), and DMSO (1.49 mL) were then added to the reaction mixture. The reaction was stirred at 50° C. for 24 h at which point the volatiles were removed under a stream of nitrogen. The resulting residue was purified by flash column chromatography (SiO₂, 0→30% acetone in hexanes) to afford the title compound (104 mg, 80%) as a colorless oil: ¹H NMR (400 MHz, CDCl₃) δ 7.34-7.28 (m, 1H), 7.22-7.14 (m, 4H), 6.84 (dt, J=11.4, 8.1 Hz, 5H), 6.57 (dd, J=12.5, 6.0 Hz, 2H), 5.73 (d, J=3.3 Hz, 1H), 4.60 (s, 2H), 3.94-3.78 (m, 3H), 3.78 (s, 3H), 1.34-1.23 (m, 4H), 0.68-0.62 (m, 2H), 0.38 (q, J=4.8 Hz, 2H); ¹⁹F NMR (376 MHz, CDCl₃) δ −112.62 (s); ESIMS m/z 459 ([M+Na]⁺).

Example 3C: Preparation of 1-((1R,2S)-1-(2-chlorophenoxy)-2-((4-methoxybenzyl)oxy)propyl)-4-fluoro-2-phenoxybenzene

To a solution of 2-((1R,2S)-1-(2-chlorophenoxy)-2-((4-methoxybenzyl)oxy)propyl)-5-fluorophenol (197 mg, 0.473 mmol), and phenylboronic acid (144 mg, 1.181 mmol) in anhydrous CH₂Cl₂ (2.36 mL) was added NEt₃ (329 μL, 2.363 mmol), Cu(OAc)₂ (94 mg, 0.520 mmol) and 4 Å molecular sieves. The reaction mixture was stirred at 23° C. for 3 days (d), and then was filtered through Celite™ and concentrated. The resulting residue was purified by flash column chromatography (SiO₂, 0→30% acetone in hexanes) to afford the title compound (102 mg, 44%) as a colorless oil: ¹HNMR (400 MHz, CDCl₃) δ 7.50 (dd, J=8.6, 6.7 Hz, 1H), 7.35 (ddd, J=10.0, 7.8, 1.8 Hz, 3H), 7.18 (dd, J=17.1, 8.0 Hz, 3H), 7.07-7.01 (m, 1H), 7.01-6.97 (m, 2H), 6.84-6.70 (m, 5H), 6.46 (dd, J=10.1, 2.4 Hz, 1H), 5.77 (d, J=3.9 Hz, 1H), 4.64 (d, J=11.8 Hz, 1H), 4.58 (d, J=11.8 Hz, 1H), 4.05-3.97 (m, 1H), 3.77 (s, 3H), 1.33 (d, J=6.4 Hz, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ −111.43 (d, J=2.1 Hz); ESIMS m/z 515 ([M+H]⁺).

Example 4A: Preparation of (1R,2S)-1-([1,1′-biphenyl]-4-yl)-1-phenoxypropan-2-ol

To a magnetically stirred mixture of 4-((1R,2S)-2-(benzyloxy)-1-phenoxypropyl)-1,1′-biphenyl (72 mg, 0.183 mmol) in ethanol (1.22 mL) and cyclohexene (608 μL) was added Pd/C (78 mg, 0.018 mmol, 2.5 wt %). The reaction mixture was stirred at 70° C. for 2 h. The reaction mixture was cooled to rt, filtered through Celite™, and concentrated. The resulting residue was purified via flash column chromatography (SiO₂, 5→30% acetone in hexanes) to afford the title compound (43 mg, 77%) as a white solid. ¹H NMR (400 MHz, CDCl₃) δ 7.59-7.54 (m, 4H), 7.43 (dd, J=12.1, 5.0 Hz, 4H), 7.33 (t, J 7.3 Hz, 1H), 7.20 (t, J 8.0 Hz, 2H), 6.90 (t, J 8.1 Hz, 3H), 5.10 (d, J 4.7 Hz, 1H), 4.20-4.12 (m, 1H), 2.00 (s, 1H), 1.29 (d, J=6.4 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 157.83, 140.92, 140.61, 136.78, 129.42, 128.78, 127.45, 127.39, 127.31, 127.05, 121.12, 115.90, 83.43, 71.14, 18.11; ESIMS m/z 631 ([2M+Na]⁺).

Example 4B: Preparation of (1S,2S)-1-phenoxy-1-(thiophen-2-yl)propan-2-ol

To a solution of 2-((1S,2S)-2-((4-methoxybenzyl)oxy)-1-phenoxypropyl)thiophene (0.223 g, 0.630 mmol) in a mixture of CH₂Cl₂ (3 mL) and H₂O (0.3 mL) at 0° C. was added 4,5-dichloro-3,6-dioxocyclohexa-1,4-diene-1,2-dicarbonitrile (0.150 g, 0.661 mmol). The reaction mixture was stirred for 30 min. The reaction was quenched by addition of aq. 1 N NaOH (0.66 mL) and was diluted with CH₂Cl₂ (10 mL). The phases were separated, and the aq. phase was extracted with CH₂Cl₂ (2×10 mL). The combined organic phases were dried over Na₂SO₄, filtered, and concentrated. Purification via flash column chromatography (SiO₂, 2→20% acetone in hexanes) afforded the title compound (116 mg, 75%) as a colorless oil: IR (Thin Film) 3390, 2923, 2851, 2865, 1597 cm⁻¹; ¹HNMR (300 MHz, CDCl₃) δ 7.33-7.16 (m, 3H), 7.07 (ddd, J=3.5, 1.2, 0.7 Hz, 1H), 7.03-6.88 (m, 4H), 5.26 (d, J=4.9 Hz, 1H), 4.28-4.09 (m, 1H), 2.08 (d, J=4.9 Hz, 1H), 1.29 (d, J=6.3 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 157.60, 140.58, 129.43, 126.59, 126.50, 125.94, 121.60, 116.21, 80.60, 70.73, 18.33.

Example 5: Preparation of (S)-(1R,2S)-1-phenoxy-1-(p-tolyl)propan-2-yl 2-((tert-butoxycarbonyl)amino)propanoate

To a solution of (1R,2S)-1-phenoxy-1-(p-tolyl)propan-2-ol (99 mg, 0.409 mmol) and (1R,2S)-1-phenoxy-1-(p-tolyl)propan-2-ol (99 mg, 0.409 mmol) in CH₂Cl₂ (2.04 mL) at 0° C. was added (S)-2-((tert-butoxycarbonyl)amino)propanoic acid (Boc-Ala-OH; 85 mg, 0.449 mmol), DMAP (4.99 mg, 0.041 mmol), and N¹-((ethylimino)methylene)-N³,N³-dimethylpropane-1,3-diamine hydrochloride (EDC; 157 mg, 0.817 mmol). The reaction mixture was stirred at rt overnight. The reaction mixture was concentrated. Purification via flash column chromatography (SiO₂, 5→30% acetone in hexanes) afforded the title compound (164 mg, 97%) as a colorless oil: ¹HNMR (400 MHz, CDCl₃) δ 7.27 (d, J=6.8 Hz, 3H), 7.19-7.11 (m, 4H), 6.87 (t, J=7.4 Hz, 1H), 6.82 (d, J=7.8 Hz, 2H), 5.28-5.21 (m, 1H), 5.15 (d, J=4.8 Hz, 1H), 4.96 (d, J=7.2 Hz, 1H), 4.29-4.19 (m, 1H), 2.31 (s, 3H), 1.42 (s, 9H), 1.35 (d, J=6.4 Hz, 3H), 1.14 (d, J=7.2 Hz, 3H); ¹³C NMR (100 MHz, CDCl₃) δ 172.73, 157.95, 137.83, 134.48, 129.33, 129.19, 126.87, 121.09, 115.96, 81.07, 74.22, 28.31, 21.15, 18.51, 14.93; ESIMS m/z 414 ([M+H]⁺).

Example 6A: Preparation of (S)-(1R,2S)-1-(4-fluorophenyl)-1-phenoxypropan-2-yl 2-aminopropanoate hydrochloride

To a solution of ((S)-(1R,2S)-1-(4-fluorophenyl)-1-phenoxypropan-2-yl 2-((tert-butoxycarbonyl)amino)propanoate (220 mg, 0.527 mmol) was added a 4 N solution of HCl in dioxane (1.98 mL, 7.9 mmol). The mixture was stirred for 1 h at rt. The solvent was evaporated under a stream of N₂ to provide the title compound as a colorless, viscous oil, which was used in the next step without further purification: ESIMS m/z 318 ([M+H]⁺).

Example 6B: Preparation of (S)-(1R,2S)-1-(4-fluorophenyl)-1-phenoxypropan-2-yl 2-(3-hydroxy-4-methoxypicolinamido)propanoate

To a solution of (S)-(1R,2S)-1-(4-fluorophenyl)-1-phenoxypropan-2-yl 2-aminopropanoate hydrochloride (186 mg, 0.526 mmol), 3-hydroxy-4-methoxypicolinic acid (98 mg, 0.578 mmol), and PyBOP (301 mg, 0.578 mmol) in CH₂Cl₂ (2.63 mL) was added N,N-diisopropylethylamine (DIEA) (303 μL, 1.74 mmol). The reaction mixture was stirred overnight at room temperature. The solvent was evaporated, and the crude oil was purified by flash column chromatography (SiO₂, 5→30% acetone in hexanes) to afford the title compound (215 mg, 80%) as a colorless oil: ¹H NMR (400 MHz, CDCl₃) δ 12.06 (s, 1H), 8.39 (d, J=7.7 Hz, 1H), 7.97 (d, J=5.2 Hz, 1H), 7.40-7.34 (m, 2H), 7.20-7.13 (m, 2H), 7.03-6.96 (m, 2H), 6.88 (dd, J=15.2, 6.3 Hz, 2H), 6.82-6.78 (m, 2H), 5.31-5.24 (m, 1H), 5.18 (d, J=5.2 Hz, 1H), 4.64 (p, J=7.2 Hz, 1H), 3.93 (s, 3H), 1.39 (d, J=6.4 Hz, 3H), 1.33 (d, J=7.2 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 171.49, 168.69, 163.72, 161.27, 157.58, 155.39, 148.76, 140.48, 133.27, 133.24, 130.37, 129.41, 128.75, 128.67, 121.41, 115.95, 115.64, 115.43, 109.49, 80.61, 74.32, 56.07, 47.95, 18.01, 15.20; ¹⁹F NMR (376 MHz, CDCl₃) δ −113.62 (s); HRMS-ESI (m/z)([M+H]⁺) calcd for C₂₅H₂₆FN₂O₆, 469.1769; found, 469.1777.

Example 7: Preparation of (S)-(1R,2S)-1-(4-fluoro-2-methoxyphenyl)-1-(p-tolyloxy)propan-2-yl 2-(3-hydroxy-4-methoxypicolinamido)propanoate

To a reaction vial was added (S)-(1R,2S)-1-(2-chloro-4-methylphenoxy)-1-(4-fluoro-2-methoxyphenyl)propan-2-yl 2-(3-hydroxy-4-methoxypicolinamido)propanoate (79 mg, 0.144 mmol), NEt₃ (60.4 μL, 0.433 mmol)), and 5% Pd/C (61.5 mg, 0.014 mmol). EtOAc (1.44 mL) was added, and the vial was sealed and stirred under approximately 1 atm (balloon) of H₂ at rt for 6.5 h. The reaction mixture was filtered through a pad of Celite™ and the filtrate was concentrated to give an oil, which was purified by flash column chromatography (SiO₂, 5→30% acetone in hexanes) to afford the title compound (66 mg, 85%) as a white foam: ¹H NMR (400 MHz, CDCl₃) δ 12.11 (s, 1H), 8.44 (d, J=7.8 Hz, 1H), 7.95 (d, J=5.2 Hz, 1H), 7.33 (dd, J=8.2, 6.8 Hz, 1H), 6.95 (d, J 8.3 Hz, 2H), 6.85 (d, J=5.2 Hz, 1H), 6.69 (t, J=5.7 Hz, 2H), 6.63-6.55 (m, 2H), 5.57 (d, J=4.6 Hz, 1H), 5.40-5.33 (m, 1H), 4.66 (p, J=7.2 Hz, 1H), 3.93 (s, 3H), 3.88 (s, 3H), 2.21 (s, 3H), 1.37 (d, J=7.2 Hz, 3H), 1.33 (d, J=6.5 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 171.43, 168.68, 163.36 (d, J=246.2 Hz), 157.81 (d, J=9.8 Hz), 155.53, 155.36, 148.76, 140.41, 130.49, 130.27, 129.77, 129.04 (d, J=10.1 Hz), 121.33 (d, J=3.2 Hz), 115.43, 109.42, 107.35 (d, J=21.3 Hz), 98.66 (d, J=25.9 Hz), 74.65, 73.23, 56.04, 55.77, 48.01, 20.42, 18.09, 15.00; ¹⁹F NMR (376 MHz, CDCl₃) δ −111.31 (s); HRMS-ESI (m/z)([M+H]⁺) calcd for C₂H₃₀FN₂O₇, 513.2032; found, 513.2027.

Example 8A: Preparation of (S)-(1R,2S)-1-phenoxy-1-(p-tolyl)propan-2-yl 2-(3-(acetoxymethoxy)-4-methoxypicolinamido)propanoate

To a suspension of (S)-(1R,2S)-1-phenoxy-1-(p-tolyl)propan-2-yl 2-(3-hydroxy-4-methoxypicolinamido)propanoate (110 mg, 0.237 mmol), and K₂CO₃ (65.5 mg, 0.474 mmol) in acetone (2.37 mL) was added bromomethyl acetate (30.2 μL, 0.308 mmol) at rt. The reaction mixture was heated to 40° C. and stirred overnight. The solvent was evaporated, and the resulting crude material was purified by flash column chromatography (SiO₂, 5→30% acetone in hexanes) to afford the title compound (94 mg, 74%) as a colorless oil: ¹H NMR (400 MHz, CDCl₃) δ 8.28 (d, J=7.8 Hz, 1H), 8.24 (d, J=5.4 Hz, 1H), 7.28 (d, J=8.0 Hz, 2H), 7.19-7.10 (m, 4H), 6.93 (d, J=5.4 Hz, 1H), 6.87 (t, J=7.4 Hz, 1H), 6.84-6.80 (m, 2H), 5.75-5.70 (m, 2H), 5.26 (dt, J=11.4, 5.7 Hz, 1H), 5.18 (d, J=5.0 Hz, 1H), 4.67 (p, J=7.2 Hz, 1H), 3.90 (s, 3H), 2.31 (s, 3H), 2.06 (s, 3H), 1.38 (d, J=6.4 Hz, 3H), 1.28 (d, J=7.2 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 172.25, 170.27, 162.95, 160.27, 157.96, 145.68, 144.01, 142.49, 137.82, 134.51, 129.31, 129.19, 126.89, 121.06, 115.98, 109.53, 89.58, 81.10, 74.38, 56.17, 48.16, 21.14, 20.87, 18.23, 15.00; HRMS-ESI (m/z)([M+H]⁺) calcd for C₂₉H₃₃N₂O₈, 537.2231; found, 537.2235.

Example 8B: Preparation of (S)-(1R,2S)-1-(2-chloro-4-methylphenoxy)-1-(4-fluoro-2-methoxyphenyl)propan-2-yl 2-(3-acetoxy-4-methoxypicolinamido)propanoate

To a solution of (S)-(1R,2S)-1-(2-chloro-4-methylphenoxy)-1-(4-fluoro-2-methoxyphenyl)propan-2-yl 2-(3-hydroxy-4-methoxypicolinamido)propanoate (59 mg, 0.108 mmol) in pyridine (539 μL, 6.58 mmol) was added acetic anhydride (539 μL, 5.61 mmol). The reaction was stirred for 1 h and then the volatiles were removed in vacuo. The resulting residue was dissolved in toluene, and the volatiles were again removed in vacuo. The resulting residue was purified via flash column chromatography (SiO₂, 5→30% acetone in hexanes) to afford the title compound (62 mg, 98%) as a white foam: ¹H NMR (400 MHz, CDCl₃) δ 8.50 (d, J=6.6 Hz, 1H), 8.28 (d, J=5.4 Hz, 1H), 7.38 (dd, J=9.2, 6.7 Hz, 1H), 7.12 (d, J=1.7 Hz, 1H), 6.98 (d, J=5.5 Hz, 1H), 6.81-6.76 (m, 1H), 6.61 (ddd, J=10.8, 5.5, 2.3 Hz, 2H), 6.55 (d, J=8.4 Hz, 1H), 5.63 (d, J=4.4 Hz, 1H), 5.42-5.35 (m, 1H), 4.72-4.64 (m, 1H), 3.90 (s, 3H), 3.88 (s, 3H), 2.39 (s, 3H), 2.19 (s, 3H), 1.35 (d, J=6.5 Hz, 3H), 1.33 (d, J=7.2 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 171.95, 168.85, 163.47 (d, J=246.5 Hz), 159.42, 162.34, 157.82 (d, J=9.7 Hz), 150.89, 146.60, 141.58, 137.48, 131.22, 130.67, 129.17 (d, J=10.1 Hz), 127.84, 122.93, 120.74 (d, J=3.4 Hz), 114.38, 109.67, 107.46 (d, J=21.3 Hz), 98.64 (d, J=25.9 Hz), 75.32, 73.02, 56.25, 55.78, 47.97, 20.71, 20.20, 18.44, 14.99; ¹⁹F NMR (376 MHz, CDCl₃) δ −110.97 (d, J=2.0 Hz); HRMS-ESI (m/z) ([M+H]⁺) calcd for C₂₉H₃₁ClFN₂O₈, 589.1747; found, 589.1749.

Example 9: Preparation of (S)-(1R,2S)-1-(4-fluoro-2-propoxyphenyl)-1-phenoxypropan-2-yl 2-(3-hydroxy-4-methoxypicolinamido)propanoate and (S)-(1R,2S)-1-(4-fluoro-2-hydroxyphenyl)-1-phenoxypropan-2-yl 2-(3-hydroxy-4-methoxypicolinamido)propanoate

To a magnetically stirred mixture of (S)-(1R,2S)-1-(2-(allyloxy)-4-fluorophenyl)-1-phenoxypropan-2-yl 2-(3-hydroxy-4-methoxypicolinamido)propanoate (91 mg, 0.173 mmol), and ruthenium chloride n-hydrate (3.91 mg, 0.017 mmol) in THF (651 μL) and water (217 μL) was added NaBH₄ (13.13 mg, 0.347 mmol) (Note—rigorous gas evolution) under a N₂ atmosphere according to the procedure of Sharma, P. K.; Kumar, S.; Kumar, P.; Nielsen, P. Tet. Lett. 2012, 48, 8704-8708. The reaction mixture was stirred at 0° C. for 1 h, at which point the reaction was carefully quenched by the addition of water and was extracted 3× with CH₂Cl₂. The combined organic extracts were dried by passing through a phase separator and volatiles were removed under a gentle stream of N₂. The resulting residue was purified via flash chromatography (SiO₂, 5→30% acetone in hexanes) to afford the title compounds (29 mg, 32%) as a colorless oil: ¹H NMR (400 MHz, CDCl₃) δ 12.12 (s, 1H), 8.43 (d, J=7.8 Hz, 1H), 7.96 (d, J=5.2 Hz, 1H), 7.32 (dd, J=8.3, 6.8 Hz, 1H), 7.20-7.13 (m, 2H), 6.86 (dd, J=10.0, 6.2 Hz, 2H), 6.82-6.77 (m, 2H), 6.61-6.53 (m, 2H), 5.62 (d, J=4.5 Hz, 1H), 5.43-5.36 (m, 1H), 4.66 (p, J=7.2 Hz, 1H), 3.98 (t, J=6.4 Hz, 2H), 3.94 (s, 3H), 1.96-1.86 (m, 2H), 1.37 (d, J=7.2 Hz, 3H), 1.34 (d, J=6.5 Hz, 3H), 1.11 (t, J=7.4 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ −111.41 (s, 1F). ¹³C NMR (101 MHz, CDCl₃) δ 171.38, 168.68, 163.33 (d, J=246.1 Hz), 157.68, 157.21 (d, J=10.0 Hz), 155.36, 148.76, 140.40, 130.49, 129.30, 128.95 (d, J=10.2 Hz), 121.10 (d, J=3.2 Hz), 120.99, 115.53, 109.42, 107.16 (d, J=21.5 Hz), 99.24 (d, J=25.9 Hz), 74.64, 73.25, 70.01, 56.04, 48.01, 22.49, 18.13, 15.03, 10.67. HRMS-ESI (m/z) ([M+H]⁺) calcd for C₂₈H₃₂FN₂O₇, 527.2188; found, 527.2188, and (33 mg, 39%) as an oily white solid: ¹H NMR (400 MHz, CDCl₃) δ 12.44 (s, 1H), 9.00 (s, 1H), 8.35 (d, J=7.6 Hz, 1H), 8.09 (d, J=5.3 Hz, 1H), 7.22 (ddd, J=8.4, 7.0, 3.6 Hz, 3H), 6.97 (d, J=5.3 Hz, 1H), 6.94 (t, J=7.3 Hz, 1H), 6.88 (d, J=7.8 Hz, 2H), 6.54 (td, J=8.4, 2.5 Hz, 1H), 6.32 (dd, J=10.0, 2.2 Hz, 1H), 5.50 (d, J=6.9 Hz, 1H), 5.20 (p, J=6.1 Hz, 1H), 4.65 (p, J=7.1 Hz, 1H), 3.99 (s, 3H), 1.51 (d, J=6.3 Hz, 3H), 1.45 (d, J=7.1 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ −112.15 (s, 1F). ¹³C NMR (101 MHz, CDCl₃) δ 170.47, 168.33, 163.09 (d, J=246.5 Hz), 157.25, 156.26, 155.47 (d, J=11.1 Hz), 149.58, 140.15, 130.12, 129.54, 128.71 (d, J=10.3 Hz), 121.77, 119.93 (d, J=3.4 Hz), 115.76, 109.65, 107.75 (d, J=21.7 Hz), 103.82 (d, J=24.0 Hz), 74.78, 56.25, 48.98, 29.26, 18.55, 16.20. HRMS-ESI (m/z) ([M+H]⁺) calcd for C₂₅H₂₆FN₂O₇, 485.1719; found, 485.1717, respectively.

Example 10A: (E)-4-fluoro-2-methoxy-1-(prop-1-en-1-yl)benzene

To a suspension of magnesium metal (486 mg, 20.0 mmol) and lithium chloride (933 mg, 22.0 mmol) in THF (20.0 mL) was added 1-bromo-4-fluoro-2-methoxybenzene (1.93 mL, 15.00 mmol) and the mixture was heated to 70° C. for 1 h at which point the reaction was cooled to 0° C. and Fe(acac)₃ (0.5 M in THF, 2.00 mL, 1.00 mmol) was added. After 1 min allyl chloride (0.814 mL, 10.0 mmol) was added and the reaction was stirred at 0° C. for 30 min, then at rt for 1 h. The reaction was then heated to 70° C. overnight. The reaction was quenched by addition of sat. NaHCO₃(aq) and diluted with petroleum ether and filtered through a pad of Celite™. The biphasic solution was extracted with petroleum ether and the combined organic phases were dried over Na₂SO₄, carefully concentrated in vacua (25° C., 250 mbar) and purified via flash column chromatography (SiO₂, 100% petroleum ether) to afford the title compound (1.07 g, 52%, 15:1 E:Z) as a colorless oil: ¹H NMR (400 MHz, CDCl₃) δ 7.31 (dd, J=8.4, 6.8 Hz, 1H), 6.66-6.51 (m, 3H), 6.14 (dq, J=15.9, 6.6 Hz, 1H), 3.82 (s, 3H), 1.88 (dd, J=6.6, 1.7 Hz, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ −113.30 (s).

Example 10B: (2S,3S)-2-(4-fluoro-2-methoxyphenyl)-3-methyloxirane

To a round-bottom flask was added buffer (0.05M Na₂B₄O₇. 10 H₂O in 4×10⁻⁴ M aqueous Na₂(EDTA), 26.5 mL), acetonitrile (40.1 mL), (E)-4-fluoro-2-methoxy-1-(prop-1-1 en-1-yo)benzene (0.55 g, 2.65 mmol), tetrabutylammonium hydrogen sulfate (0.036 g, 0.106 mmol) and 1,2,4,5-Bis-O-(isopropylidene)-β-L-erythro-2,3-hexodiulo-2,6-pyranose (Shi epoxidation catalyst enantiomer, 0.205 g, 0.794 mmol) and the reaction mixture was cooled to 0° C. A solution of Oxone (2.246 g, 3.65 mmol) in aqeuous Na₂(EDTA) (4×10⁻⁴ M, 15 mL) and a solution of potassium carbonate (2.122 g, 15.36 mmol) in water 15 mL were simultaneously added dropwise through two syringe pumps over 1.5 h. Upon completion of the syring pump additions, the reaction was immediately quenched with petroluem ether and water. The mixture was extracted 3× with petroleum ether, washed with brine, dried over Na₂SO₄, filtered and concentrated in vacuo. The resulting residue was purified via flash column chromatography (SiO₂, 0→10% acetone in hexanes) to afford the title compound (455 mg, 85%, 15:1 dr) as a colorless oil: ¹H NMR (400 MHz, CDCl₃) δ 7.06 (dd, J=8.3, 6.7 Hz, 1H), 6.67-6.52 (m, 2H), 3.89-3.80 (m, 1H), 3.84 (s, 3H), 2.91 (qd, J=5.1, 2.1 Hz, 1H), 1.45 (d, J=5.2 Hz, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ −112.15.

Example 10C: (1S,2S)-1-cyclopropoxy-1-(4-fluoro-2-methoxyphenyl)propan-2-ol and (1R,2S)-1-cyclopropoxy-1-(4-fluoro-2-methoxyphenyl)propan-2-ol

To a solution of (2S,3S)-2-(4-fluoro-2-methoxyphenyl)-3-methyloxirane (50 mg, 0.274 mmol), in cyclopropanol (1.37 mL) was added sulfuric (1 drop). The reaction mixture was stirred at 0° C. for 10 min then quenched by addition of solid K₂CO₃. Volatiles were removed under a gentle stream of N₂ and the resulting residue was purified via flash chromatography (SiO2, 5→30% acetone in hexanes) to yield the title compounds as two diastereomers: Major (1S,2S) (32 mg, 49%): ¹H NMR (400 MHz, CDCl₃) δ 7.31 (dd, J=8.4, 6.9 Hz, 1H), 6.69 (td, J=8.3, 2.4 Hz, 1H), 6.62 (dd, J=10.9, 2.4 Hz, 1H), 4.62 (d, J=7.5 Hz, 1H), 3.82 (s, 3H), 3.78 (dt, J=13.2, 4.6 Hz, 1H), 3.16 (dq, J=9.1, 3.0 Hz, 1H), 2.62 (s, 1H), 0.99 (d, J=6.4 Hz, 3H), 0.66-0.50 (m, 2H), 0.40 (dddd, J=16.3, 14.5, 10.4, 6.2 Hz, 2H); ¹⁹F NMR (376 MHz, CDCl₃) δ −112.05 (s); ESIMS m/z 263 ([M+Na]⁺). Minor (1R,2S) (18 mg, 27%): ¹H NMR (400 MHz, CDCl₃) δ 7.38 (dd, J=8.4, 7.0 Hz, 1H), 6.70 (td, J=8.4, 2.4 Hz, 1H), 6.61 (dd, J=10.9, 2.4 Hz, 1H), 4.83 (d, J=4.2 Hz, 1H), 4.00-3.91 (m, 1H), 3.82 (s, 3H), 3.24 (dq, J=9.2, 3.0 Hz, 1H), 1.94 (d, J=6.2 Hz, 1H), 1.00 (d, J=6.5 Hz, 3H), 0.70-0.63 (m, 1H), 0.59-0.52 (m, 1H), 0.51-0.43 (m, 1H), 0.42-0.35 (m, 1H); ¹⁹F NMR (376 MHz, CDCl₃) δ −112.65 (s); ESIMS m/z 263 ([M+Na]⁺).

Example A: Evaluation of Fungicidal Activity: Leaf Blotch of Wheat (Zymoseptoria tritici; Bayer Code SEPTTR)

Technical grades of materials were dissolved in acetone, which were then mixed with nine volumes of water containing 110 ppm Triton X-100. The fungicide solutions were applied onto wheat seedlings using an automated booth sprayer to run-off. All sprayed plants were allowed to air dry prior to further handling. All fungicides were evaluated using the aforementioned method for their activity vs. all target diseases, unless stated otherwise. Wheat leaf blotch and brown rust activity were also evaluated using track spray applications, in which case the fungicides were formulated as EC formulations, containing 0.1% Trycol 5941 in the spray solutions.

Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Zymoseptoria tritici either prior to or after fungicide treatments. After inoculation the plants were kept in 100% relative humidity (one day in a dark dew chamber followed by two to three days in a lighted dew chamber at 20° C.) to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 20° C. for disease to develop. When disease symptoms were fully expressed on the 1^(st) leaves of untreated plants, infection levels were assessed on a scale of 0 to 100 percent disease severity. Percent disease control was calculated using the ratio of disease severity on treated plants relative to untreated plants.

Example B: Evaluation of Fungicidal Activity: Wheat Brown Rust (Puccinia triticina; Synonym: Puccinia recondita f. sp. tritici; Bayer code PUCCRT)

Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Puccinia triticina either prior to or after fungicide treatments. After inoculation the plants were kept in a dark dew room at 22° C. with 100% relative humidity overnight to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 24° C. for disease to develop. Fungicide formulation, application and disease assessment followed the procedures as described in the Example A.

Example C: Evaluation of Fungicidal Activity: Wheat Glume Blotch (Leptosphaeria nodorum; Bayer Code LEPTNO)

Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Leptosphaeria nodorum 24 hr after fungicide treatments. After inoculation the plants were kept in 100% relative humidity (one day in a dark dew chamber followed by two days in a lighted dew chamber at 20° C.) to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 20° C. for disease to develop. Fungicide formulation, application and disease assessment followed the procedures as described in the Example A.

Example D: Evaluation of Fungicidal Activity: Apple Scab (Venturia inaequalis; Bayer code VENTIN)

Apple seedlings (variety McIntosh) were grown in soil-less Metro mix, with one plant per pot. Seedlings with two expanding young leaves at the top (older leaves at bottom of the plants were trimmed) were used in the test. Plants were inoculated with a spore suspension of Venturia inaequalis 24 hr after fungicide treatment and kept in a 22° C. dew chamber with 100% relative humidity for 48 hr, and then moved to a greenhouse set at 20° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example E: Evaluation of Fungicidal Activity: Leaf Spot of Sugar Beets (Cercospora beticola; Bayer Code CERCBE)

Sugar beet plants (variety HH88) were grown in soil-less Metro mix and trimmed regularly to maintain a uniform plant size prior to test. Plants were inoculated with a spore suspension 24 hr after fungicide treatments. Inoculated plants were kept in a dew chamber at 22° C. for 48 hr then incubated in a greenhouse set at 24° C. under a clear plastic hood with bottom ventilation until disease symptoms were fully expressed. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example F: Evaluation of Fungicidal Activity: Asian Soybean Rust (Phakopsora pachyrhizi; Bayer Code PHAKPA)

Technical grades of materials were dissolved in acetone, which were then mixed with nine volumes of water containing 0.011% Tween 20. The fungicide solutions were applied onto soybean seedlings using an automated booth sprayer to run-off. All sprayed plants were allowed to air dry prior to further handling.

Soybean plants (variety Williams 82) were grown in soil-less Metro mix, with one plant per pot. Two weeks old seedlings were used for testing. Plants were inoculated either 3 days prior to or 1 day after fungicide treatments. Plants were incubated for 24 h in a dark dew room at 22° C. and 100% relative humidity then transferred to a growth room at 23° C. for disease to develop. Disease severity was assessed on the sprayed leaves.

Example G: Evaluation of Fungicidal Activity: Barley Scald (Rhyncosporium secalis; Bayer code RHYNSE)

Barley seedlings (variety Harrington) were propagated in soil-less Metro mix, with each pot having 8 to 12 plants, and used in the test when first leaf was fully emerged. Test plants were inoculated by an aqueous spore suspension of Rhyncosporium secalis 24 hr after fungicide treatments. After inoculation the plants were kept in a dew room at 22° C. with 100% relative humidity for 48 hr. The plants were then transferred to a greenhouse set at 20° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example H: Evaluation of Fungicidal Activity: Rice Blast (Pyricularia oryzae; Bayer Code PYRIOR)

Rice seedlings (variety Japonica) were propagated in soil-less Metro mix, with each pot having 8 to 14 plants, and used in the test when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Pyricularia oryzae 24 hr after fungicide treatments. After inoculation the plants were kept in a dew room at 22° C. with 100% relative humidity for 48 hr to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse set at 24° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example I: Evaluation of Fungicidal Activity: Tomato Early Blight (Alternaria solani; Bayer code ALTESO)

Tomato plants (variety Outdoor Girl) were propagated in soil-less Metro mix, with each pot having one plant, and used when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Alternaria solani 24 hr after fungicide treatments. After inoculation the plants were kept in a dew room at 22° C. with 100% relative humidity for 48 hr to permit spores to germinate and infect the leaf. The plants were then transferred to a growth room at 22° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

Example J: Evaluation of Fungicidal Activity: Cucumber Anthracnose (Colletotrichum Lagenarium; Bayer Code COLLLA)

Cucumber seedlings (variety Bush Pickle) were propagated in soil-less Metro mix, with each pot having one plant, and used in the test when 12 to 14 days old. Test plants were inoculated with an aqueous spore suspension of Colletotrichum lagenarium 24 hr after fungicide treatments. After inoculation the plants were kept in a dew room at 22° C. with 100% relative humidity for 48 hr to permit spores to germinate and infect the leaf. The plants were then transferred to a growth room set at 22° C. for disease to develop. Fungicide formulation, application and disease assessment on the sprayed leaves followed the procedures as described in the Example A.

TABLE 1 Compound Structure, Appearance, and Preparation Method Prepared According *Cmpd. to Colorless No. Structure Example Semi-Solid  1

Example 1A; Example 2C; Example 4A; Example 5 Colorless Semi-Solid  2

Example 1A; Example 2A; Example 4B; Example 5 White Solid  3

Example 1A; Example 2A; Example 4B; Example 5 Sticky Oil  4

Example 1A; Example 2B; Example 4A; Example 5 Sticky Oil  5

Example 1A; Example 2B; Example 4A; Example 5 Sticky Oil  6

Example 1A; Example 2B; Example 4A; Example 5 Sticky Oil  7

Example 1A; Example 2B; Example 4A; Example 5 Sticky Oil  8

Example 1A; Example 2B; Example 4A; Example 5 Sticky Oil  9

Example 1A; Example 2A; Example 4A; Example 5 Sticky Wax  10

Example 1A; Example 2A; Example 4A; Example 5 Sticky Wax  11

Example 1A; Example 2B; Example 4A; Example 5 Sticky Oil  12

Example 1A; Example 2B; Example 4A; Example 5 White Solid  13

Example 1A; Example 2B; Example 4A; Example 5 Sticky Glass  14

Example 1A; Example 2B; Example 4A; Example 5 Sticky Glass  15

Example 1A; Example 2B; Example 4A; Example 5 Sticky Oil  16

Example 1A; Example 2B; Example 4A; Example 5 Semi-Solid  17

Example 1A; Example 2C; Example 4A; Example 5 Colorless Oil  18

Example 1A; Example 2C; Example 4A; Example 5 Colorless Oil  19

Example 1D; Example 2A; Example 4B; Example 5 Colorless Oil  20

Example 1D; Example 2A; Example 4B; Example 5 Colorless Oil  21

Example 1B; Example 1C; Example 2B; Example 4A; Example 5 Colorless Oil  22

Example 1D; Example 2A; Example 4B; Example 5 Colorless Oil  23

Example 1D; Example 2A; Example 4B; Example 5 Colorless Oil  24

Example 1B; Example 1C; Example 2C; Example 4A; Example 5 Colorless Oil  25

Example 1B; Example 1C; Example 2C; Example 4A; Example 5 Colorless Oil  26

Example 1B; Example 1C; Example 2C; Example 4A; Example 5 Colorless Oil  27

Example 1B; Example 1C; Example 2C; Example 4A; Example 5 Colorless Oil  28

Example 1B; Example 1C; Example 2C; Example 4A; Example 5 Colorless Oil  29

Example 1B; Example 1C; Example 2C; Example 4A; Example 5 Colorless Oil  30

Example 1B; Example 1C; Example 2C; Example 4A; Example 5 Colorless Oil  31

Example 1B; Example 1C; Example 2C; Example 4A; Example 5 Colorless Oil  32

Example 1A; Example 2A; Example 4A; Example 5 Colorless Oil  33

Example 1A; Example 2A; Example 4A; Example 5 Colorless Oil  34

Example 1A; Example 2A; Example 4B; Example 5 Colorless Oil  35

Example 1A; Example 2A; Example 4A; Example 5 Colorless Oil  36

Example 1A; Example 2A; Example 4A; Example 5 Colorless Oil  37

Example 1A; Example 2B; Example 4A; Example 5 Colorless Oil  38

Example 1A; Example 2B; Example 4A; Example 5 Colorless Oil  39

Example 1A; Example 2A; Example 4A; Example 5 Colorless Oil  40

Example 1A; Example 2A; Example 4B; Example 5 Colorless Oil  41

Example 1A; Example 2A; Example 4B; Example 5 Colorless Oil  42

Example 1A; Example 2A; Example 4B; Example 5 Colorless Oil  43

Example 1A; Example 2B; Example 4B; Example 5 Colorless Oil  44

Example 1A; Example 2A; Example 4A; Example 5 Colorless Oil  45

Example 1A; Example 2A; Example 4A; Example 5 Colorless Oil  46

Example 1A; Example 2A; Example 4B; Example 5 Colorless Oil  47

Example 1A; Example 2A; Example 4B; Example 5 White Waxy Solid  48

Example 1A; Example 2A; Example 4B; Example 5 Colorless Oil  49

Example 1E; Example 2A; Example 4B; Example 5 Colorless Oil  50

Example 1A; Example 2A; Example 4B; Example 5 Colorless Oil  51

Example 1A; Example 2A; Example 4B; Example 5 White Foam  52

Example 1E; Example 2A; Example 4B; Example 5 Foamy Solid  53

Example 1E; Example 2B; Example 4B; Example 5 Colorless Oil  54

Example 1E; Example 2A; Example 4B; Example 5 Colorless Oil  56

Example 1E; Example 2A; Example 4B; Example 5 White Foam  57

Example 1E; Example 2B; Example 4B; Example 5 White Foam  58

Example 1E; Example 2B; Example 4B; Example 5 Colorless Oil  59

Example 1E; Example 2A; Examples 3A,B; Example 4B; Example 5 White Solid  60

Example 1E; Example 2A; Examples 3A,B; Example 4B; Example 5 Colorless Oil  61

Example 1E; Example 2B; Examples 3A,C; Example 4B; Example 5 Colorless Oil  62

Example 6, Step 1 White Solid  63

Example 6, Step 1 White Solid  64

Example 6, Step 1 Clear Glass  65

Example 6, Step 1 Clear Glass  66

Example 6, step 1 White Powder  67

Example 6, step 1 White Powder  68

Example 6, step 1 White Powder  69

Example 6, step 1 White Powder  70

Example 6, step 1 White Powder  71

Example 6, step 1 White Powder  72

Example 6, step 1 White Powder  73

Example 6, step 1 White Powder  74

Example 6, step 1 White Powder  75

Example 6, step 1 White Powder  76

Example 6, step 1 White Powder  77

Example 6, step 1 White Powder  78

Example 6, step 1 Colorless Oil  79

Example 6, step 1 Colorless Oil  80

Example 6, Step 1 Colorless Oil  81

Example 6, step 1 Colorless Oil  82

Example 6, Step 1 Colorless Oil  83

Example 6, Step 1 Colorless Oil  84

Example 6, step 1 Beige Solid  85

Example 6, step 1 Colorless Oil  86

Example 6, Step 1 Colorless Oil  87

Example 6, Step 1 Colorless Oil  88

Example 6, Step 1 Colorless Oil  89

Example 6, Step 1 Colorless Oil  90

Example 6, step 1 Colorless Viscous Oil  91

Example 6, step 1 Colorless Oil  92

Example 6, step 1 Oily White Solid  93

Example 6, step 1 Colorless Oil  94

Example 6, step 1 Colorless Oil  95

Example 6, Step 1 Colorless Oil  96

Example 6, Step 1 Colorless Oil  97

Example 6, Step 1 Colorless Oil  98

Example 6, step 1 Colorless Oil  99

Example 6, step 1 Clear Viscous Oil 100

Example 6, step 1 Colorless Viscous Oil 101

Example 6, step 1 Colorless Oil 102

Example 6, step 1 Colorless Oil 103

Example 6, step 1 Colorless Oil 104

Example 6, step 1 Colorless Oil 105

Example 6, step 1 Oily White Solid 106

Example 6, step 1 Colorless Oil 107

Example 6, step 1 Colorless Oil 108

Example 6, step 1 Oily White Solid 109

Example 6, step 1 White Solid 110

Example 6, step 1 Colorless Oil 111

Example 6, step 1 Colorless Oil 112

Example 6, step 1 Colorless Oil 113

Example 6, Steps 1, 2 Colorless Semi-Solid 114

Example 6, Step 2 White Solid 115

Example 6, Step 2 White Foam 116

Example 6, Step 2 Whiote Foam 117

Example 6, Step 2 White Powder 118

Example 6, Step 2 White Powder 119

Example 6, Step 2 White Powder 120

Example 6, Step 2 White Powder 121

Example 6, Step 2 Hygroscopic White Powder 122

Example 6, Step 2 Hygroscopic White Powder 123

Example 6, Step 2 Hygroscopic White Powder 124

Example 6, Step 2 Hygroscopic White Powder 125

Example 6, Step 2 White Powder 126

Example 6, Step 2 White Powder 127

Example 6, Step 2 Hygroscopic White Powder 128

Example 6, Step 2 White Powder 129

Example 6, Steps 1, 2 Colorless Oil 130

Example 6, Steps 1, 2 Colorless Oil 131

Example 6, Step 2 Colorless Oil 132

Example 6, Steps 1, 2 Colorless Foam/Oil 133

Example 6, Step 2 Foamy White Solid 134

Example 6, Step 2 White Foam 135

Example 7A Colorless Oil 136

Example 6, Step 2 Colorless Oil 137

Example 6, Step 2 Colorless Oil 138

Example 6, Steps 1, 2 Colorless Oil 139

Example 6, Steps 1, 2 Colorless Oil 140

Example 6, Steps 1, 2 Colorless Oil 141

Example 6, Steps 1, 2 Colorless Oil 142

Example 6, Steps 1, 2 Colorless Oil 143

Example 6, Step 2 Beige Solid 144

Example 6, Step 2 Colorless Oil 145

Example 6, Step 2 Colorless Oil 146

Example 6, Step 2 Colorless Oil 147

Example 6, Step 2 Colorless Oil 148

Example 6, Step 2 Colorless Oil 149

Example 6, Step 2 Colorless Oil 150

Example 6, Step 2 Colorless Oil 151

Example 7A Colorless Oil 152

Example 7A Colorless Oil 153

Example 6, Step 2 Colorless Oil 154

Example 6, Step 2 Viscous Foam 155

Example 6, Step 2 Colorless Oil 156

Example 6, Step 2 Colorless Oil 157

Example 7A Colorless Oil 158

Example 6, Step 2 Colorless Foam 159

Example 6, Step 2 Colorless Foam 160

Example 6, Step 2 Colorless Oil 161

Example 6, Step 2 Colorless Oil 162

Example 6, Step 2 Colorless Oil 163

Example 6, Step 2 Colorless Foamy Oil 164

Example 6, Step 2 Colorless Oil 165

Example 6, Step 2 White Foam 166

Example 6, Step 2 White Foam 167

Example 6, Step 2 Foamy White Solid 168

Example 6, Step 2 White Foam 169

Example 6, Step 2 White Foam 170

Example 6, Step 2; Example 7B Oily White Solid 171

Example 6, Step 2; Example 7B Colorless Oil 172

Example 6, Step 2 White Foam 173

Example 6, Step 2; Example 7A White Foam 174

Example 6, Step 2 White Foamy Solid 175

Example 6, Step 2 Colorless Oil 176

Example 6, Step 2 Colorless Oil 177

Example 6, Step 2; Example 7A Colorless Oil 178

Example 6, Step 2; Example 7A White Foam 179

Example 6, Step 2 White Foam 180

Example 6, Step 2 Colorless Oil 181

Example 6, Step 2 Colorless Oil 182

Example 8A Light Yellow Semi-Solid 183

Example 8A Yellow Solid 184

Example 8B White Solid 185

Example 8A White Foam 186

Example 8A White Foam 187

Example 8A White Powder 188

Example 8B White Powder 189

Example 8A White Powder 190

Example 8B White Powder 191

Example 8A White Powder 192

Example 8B White Powder 193

Example 8A Hygroscopic Solid 194

Example 8B White Powder 195

Example 8A White Powder 196

Example 8B White Powder 197

Example 8A Hygroscopic Powder 198

Example 8B White Powder 199

Example 8A White Powder 200

Example 8B White Powder 201

Example 8A White Powder 202

Example 8A Sticky Oil 203

Example 8B White Powder 204

Example 8A White Powder 205

Example 8B White Powder 206

Example 8A Semi-Solid 207

Example 8B White Powder 208

Example 8A Sticky White Solid 209

Example 8B White Powder 210

Example 8B Colorless Oil 211

Example 8B Colorless Oil 212

Example 8B Colorless Foam/Oil 213

Example 8A Colorless Foam/Oil 214

Example 8B Colorless Oil 215

Example 8B Colorless Oil 216

Example 8A Colorless Oil 217

Example 8B Colorless Oil 218

Example 8B Colorless Oil 219

Example 8A Colorless Oil 220

Example 8A Colorless Oil 221

Example 8A Colorless Oil 222

Example 8B Colorless Oil 223

Example 8B Off White Foam 224

Example 8B Colorless Oil 225

Example 8B Colorless Oil 226

Example 8A Colorless Oil 227

Example 8B Colorless Oil 228

Example 8B Colorless Oil 229

Example 8B Colorless Oil 230

Example 8A Colorless Oil 231

Example 8B Colorless Oil 232

Example 8B Colorless Oil 233

Example 8B Colorless Oil 234

Example 8A Colorless Oil 235

Example 8B Colorless Oil 236

Example 8B Colorless Oil 237

Example 8A Colorless Oil 238

Example 8A Colorless Oil 239

Example 8A Colorless Oil 240

Example 8A Colorless Oil 241

Example 8A Colorless Oil 242

Example 8B Light Yellow Oil 243

Example 8B Colorless Oil 244

Example 8A Colorless Oil 245

Example 8A Colorless Oil 246

Example 8B Colorless Oil 247

Example 8B Colorless Oil 248

Example 8A Colorless Oil 249

Example 8A Colorless Oil 250

Example 8A Colorless Oil 251

Example 8B Faint Yellow Oil 252

Example 8A Colorless Oil 253

Example 8A Colorless Oil 254

Example 8A Colorless Oil 255

Example 8A Colorless Oil 256

Example 8A Faint Yellow Oil 257

Example 8A Colorless Oil 258

Example 8A Colorless Oil 259

Example 8A Colorless Oil 260

Example 8A Colorless Oil 261

Example 8A White Foam 262

Example 8A White Foam 263

Example 8A White Foam 264

Example 8B White Foam 265

Example 8B White Foam 266

Example 8B White Foam 267

Example 8B White Foam 268

Example 8B White Foam 269

Example 8B Off White Foam 270

Example 8B White Foam 271

Example 8B White Foam 272

Example 8B Colorless Oil 273

Example 8B Colorless Oil 274

Example 8B White Foam 275

Example 8B White Foam 276

Example 6A White Oily Solid 277

Example 6A Colorless Oil 278

Example 6A Colorless Oil 279

Example 6A Colorless Oil 280

Example 6A Colorless Oil 281

Example 6A Colorless Oil 282

Example 1E; Example 2C; Example 4B; Example 5 Colorless Oil 283

Example 1E; Example 2C; Example 4B; Example 5 Colorless Oil 284

Example 1E; Example 2D; Example 4B; Example 5 Colorless Oil 285

Example 1E; Example 2D; Example 4B; Example 5 Colorless Oil 286

Examples 10A-C; Example 5 Colorless Oil 287

Examples 10A-C; Example 5 Colorless Oil 288

Example 6B Colorless Oil 289

Example 6B Colorless Oil 290

Example 6B Colorless Oil 291

Example 6B Oily White Solid 292

Example 6B White Wax 293

Example 6B Colorless Oil 294

Example 8B White Foam 295

Example 8B White Foam 296

Example 8B White Foam 297

Example 8B White Foam 298

Example 8B Off White Foam 299

Example 8B Colorless Oil

TABLE 2 Analytical Data *Cmpd. NMR No. IR (cm⁻¹) MASS (¹H, ¹³C or ¹⁹F) 1 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 7.36-7.22 [M]⁺ calcd for (m, 5H), 5.09 (p, J = 6.3 Hz, C₂₁H₃₁NO₅, 1H), 5.01-4.93 (m, 1H), 4.31 (d, J = 377.2202; found, 6.2 Hz, 1H), 4.23-4.13 (m, 1H), 377.2206 3.19 (d, J = 6.8 Hz, 2H), 1.42 (s, 9H), 1.32 (d, J = 6.4 Hz, 3H), 1.04 (d, J = 7.2 Hz, 3H), 1.03-0.96 (m, 1H), 0.54-0.40 (m, 2H), 0.19-0.04 (m, 2H). ¹³C NMR (126 MHz, CDCl₃) δ 172.47, 154.95, 138.76, 128.21, 127.95, 127.59, 83.05, 79.63, 74.05, 73.71, 49.19, 28.32, 18.43, 16.01, 10.58, 3.19, 2.71. 2 ESIMS m/z 400 ¹H NMR (400 MHz, CDCl₃) δ 7.43-7.22 ([M + H]⁺) (m, 5H), 7.23-7.12 (m, 2H), 6.93-6.78 (m, 3H), 5.26 (qd, J = 6.3, 4.8 Hz, 1H), 5.18 (d, J = 5.0 Hz, 1H), 4.97 (d, J = 8.2 Hz, 1H), 4.24 (h, J = 7.4, 6.8 Hz, 1H), 1.42 (s, 9H), 1.37 (d, J = 6.4 Hz, 3H), 1.12 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.72, 157.90, 137.59, 129.37, 128.52, 128.15, 126.97, 126.80, 121.20, 115.98, 81.23, 79.75, 74.16, 49.28, 28.32, 18.45, 15.04. 3 ESIMS m/z 456 ¹H NMR (400 MHz, CDCl₃) δ 7.39-7.30 ([M + Na]⁺) (m, 5H), 7.16-7.09 (m, 2H), 6.79-6.71 (m, 2H), 5.25 (qd, J = 6.5, 4.8 Hz, 1H), 5.13 (d, J = 4.9 Hz, 1H), 4.94 (d, J = 8.0 Hz, 1H), 4.24 (t, J = 7.6 Hz, 1H), 1.42 (s, 9H), 1.35 (d, J = 6.4 Hz, 3H), 1.13 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.71, 156.42, 155.02, 137.00, 129.28, 128.62, 128.36, 126.90, 126.13, 117.25, 81.62, 79.82, 73.96, 49.25, 28.30, 18.46, 14.90. 4 ESIMS m/z 434 ¹H NMR (400 MHz, CDCl₃) δ 7.41-7.26 ([M + H]⁺) (m, 5H), 7.08 (ddd, J = 8.4, 7.7, 0.6 Hz, 1H), 6.91-6.82 (m, 2H), 6.70 (ddd, J = 8.4, 2.4, 1.0 Hz, 1H), 5.30-5.19 (m, 1H), 5.16 (d, J = 4.9 Hz, 1H), 4.95 (d, J = 8.3 Hz, 1H), 4.28-4.19 (m, 1H), 1.42 (s, 9H), 1.35 (d, J = 6.5 Hz, 3H), 1.14 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.71, 158.54, 155.01, 136.85, 134.75, 130.15, 128.65, 128.40, 126.87, 121.47, 116.59, 114.09, 81.48, 79.81, 73.95, 49.26, 28.30, 18.44, 14.89. 5 ESIMS m/z 456 ¹H NMR (400 MHz, CDCl₃) δ 7.44-7.26 ([M + Na])⁺ (m, 6H), 7.00 (ddd, J = 8.3, 7.5, 1.7 Hz, 1H), 6.82 (td, J = 7.7, 1.4 Hz, 1H), 6.66 (dd, J = 8.3, 1.4 Hz, 1H), 5.36-5.22 (m, 2H), 4.97 (d, J = 8.2 Hz, 1H), 4.29-4.20 (m, 1H), 1.45-1.39 (m, 12H), 1.15 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.71, 155.00, 153.31, 136.81, 130.34, 128.61, 128.39, 127.44, 126.90, 123.54, 121.78, 115.14, 82.01, 79.75, 74.19, 49.30, 28.30, 18.43, 14.86. 6 ESIMS m/z 436 ¹H NMR (500 MHz, CDCl₃) δ 7.42-7.27 ([M + H]⁺) (m, 5H), 6.98 (ddd, J = 10.6, 9.0, 5.3 Hz, 1H), 6.58-6.44 (m, 2H), 5.30 (qd, J = 6.4, 5.0 Hz, 1H), 5.17 (d, J = 5.0 Hz, 1H), 4.95 (d, J = 8.0 Hz, 1H), 4.24 (t, J = 7.7 Hz, 1H), 1.42 (s, 9H), 1.39 (d, J = 6.4 Hz, 3H), 1.14 (d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.66, 158.32 (dd, J = 242.4, 2.5 Hz), 155.00, 149.47 (dd, J = 242.1, 3.4 Hz), 146.24 (dd, J = 12.1, 10.8 Hz), 136.27, 128.69, 128.66, 126.99, 116.41 (dd, J = 20.8, 10.1 Hz), 107.68 (dd, J = 24.0, 6.9 Hz), 105.12 (dd, J = 27.2, 1.7 Hz), 83.04, 79.80, 73.72, 49.25, 28.29, 18.35, 15.03. 7 ESIMS m/z 468 ¹H NMR (500 MHz, CDCl₃) δ 7.40-7.28 ([M + H]⁺) (m, 6H), 6.97 (dd, J = 8.8, 2.6 Hz, 1H), 6.57 (d, J = 8.9 Hz, 1H), 5.30 (qd, J = 6.4, 4.6 Hz, 1H), 5.21 (d, J = 4.6 Hz, 1H), 4.96 (d, J = 8.1 Hz, 1H), 4.29-4.22 (m, 1H), 1.43-1.39 (m, 12H), 1.16 (d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.70, 155.00, 152.06, 136.27, 130.04, 128.71, 128.59, 127.36, 126.86, 126.20, 124.35, 115.83, 82.37, 79.80, 73.97, 49.27, 28.29, 18.43, 14.82. 8 ESIMS m/z 452 ¹H NMR (500 MHz, CDCl₃) δ 7.38-7.30 ([M + H]⁺) (m, 5H), 6.68-6.60 (m, 2H), 6.48-6.40 (m, 1H), 5.29-5.20 (m, 1H), 5.14 (d, J = 4.7 Hz, 1H), 4.94 (d, J = 8.2 Hz, 1H), 4.28-4.21 (m, 1H), 1.42 (s, 9H), 1.34 (d, J = 6.5 Hz, 3H), 1.15 (d, J = 7.3 Hz, 3H). ¹H NMR (500 MHz, CDCl₃) δ 7.38-7.30 (m, 5H), 6.68-6.60 (m, 2H), 6.48-6.40 (m, 1H), 5.29-5.20 (m, 1H), 5.14 (d, J = 4.7 Hz, 1H), 4.94 (d, J = 8.2 Hz, 1H), 4.28-4.21 (m, 1H), 1.42 (s, 9H), 1.34 (d, J = 6.5 Hz, 3H), 1.15 (d, J = 7.3 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.69, 163.12 (d, J = 248.4 Hz), 159.25 (d, J = 12.4 Hz), 155.00, 136.22, 135.29 (d, J = 13.3 Hz), 128.78, 128.62, 126.80, 112.55 (d, J = 3.3 Hz), 109.25 (d, J = 25.2 Hz), 102.25 (d, J = 25.0 Hz), 81.78, 79.86, 73.72, 49.24, 28.29, 18.43, 14.82. 9 (Thin film) HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 7.42-7.37 3364.14, 2978.73, ([M + Na]⁺) calcd for (m, 2H), 7.37-7.30 (m, 2H), 1709.99, 1492.42, C₂₃H₂₉NNaO₅, 7.31-7.22 (m, 1H), 7.22-7.14 (m, 1235.09, 1160.57 422.1938; found, 2H), 6.92-6.81 (m, 3H), 5.29-5.20 422.1940 (m, 2H), 4.93 (d, J = 8.0 Hz, 1H), 4.31-4.16 (m, 1H), 1.43 (s, 9H), 1.37-1.31 (m, 3H), 1.28 (d, J = 7.2 Hz, 3H). 10 (Thin film) HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 7.41-7.37 3366.73, 1708.90, ([M + Na]⁺) calcd for (m, 2H), 7.36-7.30 (m, 2H), 1492.33, 1236.49, C₂₃H₂₉NNaO₅, 7.29-7.23 (m, 1H), 7.21-7.12 (m, 1159.90 422.1938; found, 2H), 6.90-6.85 (m, 1H), 6.85-6.80 422.1939 (m, 2H), 5.26 (dq, J = 6.2, 4.8 Hz, 1H), 5.18 (d, J = 5.0 Hz, 1H), 4.97 (d, J = 8.3 Hz, 1H), 4.31-4.16 (m, 1H), 1.42 (s, 9H), 1.37 (d, J = 6.4 Hz, 3H), 1.12 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.72, 157.90, 155.00, 137.59, 129.37, 128.53, 128.16, 126.97, 121.20, 115.98, 81.23, 79.76, 74.17, 49.28, 28.32, 18.45, 15.04. 11 ESIMS m/z 467 ¹H NMR (400 MHz, CDCl₃) δ 7.41-7.27 ([M + H]⁺) (m, 5H), 6.68-6.59 (m, 2H), 6.43 (dt, J = 10.4, 2.3 Hz, 1H), 5.29-5.18 (m, 1H), 5.14 (d, J = 4.7 Hz, 1H), 4.96 (d, J = 8.2 Hz, 1H), 4.22 (q, J = 6.8 Hz, 1H), 1.73-1.61 (m, 1H), 1.54-1.40 (m, 10H), 1.33 (d, J = 6.4 Hz, 3H), 0.72 (t, J = 7.5 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.06, 163.12 (d, J = 248.2 Hz), 159.24 (d, J = 12.4 Hz), 155.27, 136.21, 135.29 (d, J = 13.3 Hz), 128.80, 128.63, 126.78, 112.54 (d, J = 3.3 Hz), 109.24 (d, J = 25.2 Hz), 102.23 (d, J = 25.1 Hz), 81.77, 79.80, 73.79, 54.48, 28.30, 25.65, 14.81, 9.14. ¹⁹F NMR (376 MHz, CDCl₃) δ-109.89. 12 ESIMS m/z 473 ¹H NMR (400 MHz, CDCl₃) δ 7.43-7.28 ([M + Na]⁺) (m, 5H), 6.98 (ddd, J = 10.6, 9.0, 5.3 Hz, 1H), 6.59-6.42 (m, 2H), 5.29 (qd, J = 6.4, 4.8 Hz, 1H), 5.17 (d, J = 4.9 Hz, 1H), 4.97 (d, J = 8.3 Hz, 1H), 4.22 (q, J = 6.8 Hz, 1H), 1.72-1.58 (m, 1H), 1.48-1.36 (m, 13H), 0.69 (t, J = 7.5 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.01, 158.32 (dd, J = 242.4, 2.5 Hz), 155.25, 149.44 (dd, J = 242.0, 3.3 Hz), 146.24 (dd, J = 12.3, 10.6 Hz), 136.29, 128.71, 128.66, 126.94, 116.38 (dd, J = 20.8, 10.2 Hz), 107.66 (d, J = 24.0 Hz), 105.03 (dd, J = 27.3, 1.4 Hz), 83.01, 79.74, 73.84, 54.48, 28.30, 25.61, 15.03, 9.05. ¹⁹F NMR (376 MHz, CDCl₃) δ-116.68 (d, J = 15.0 Hz), −138.71 (d, J = 15.0 Hz). 13 ESIMS m/z 469 ¹H NMR (500 MHz, CDCl₃) δ 7.47-7.41 ([M + H]⁺) (m, 2H), 7.40-7.27 (m, 5H), 6.92-6.86 (m, 2H), 5.32-5.21 (m, 2H), 4.94 (d, J = 8.1 Hz, 1H), 4.25 (t, J = 7.6 Hz, 1H), 1.41 (s, 9H), 1.37 (d, J = 6.3 Hz, 3H), 1.14 (d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.72, 160.16, 155.00, 136.58, 128.73, 128.51, 126.85 (q, J = 3.7 Hz), 126.83, 124.25 (q, J = 271.2 Hz), 123.34 (q, J = 32.6 Hz), 115.78, 81.32, 79.85, 73.87, 49.26, 28.29, 18.43, 14.84. ¹⁹F NMR (471 MHz, CDCl₃) δ-61.67. 14 ESIMS m/z 497 ¹H NMR (500 MHz, CDCl₃) δ 7.47-7.40 ([M + H]⁺) (m, 2H), 7.40-7.28 (m, 5H), 6.91-6.84 (m, 2H), 5.32-5.23 (m, 2H), 4.93 (d, J = 9.3 Hz, 1H), 4.19 (dd, J = 9.2, 4.5 Hz, 1H), 2.01-1.90 (m, 1H), 1.42 (s, 9H), 1.36 (d, J = 6.2 Hz, 3H), 0.84 (d, J = 6.8 Hz, 3H), 0.62 (d, J = 6.8 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.85, 160.12, 155.66, 136.53, 128.78, 128.50, 126.82 (q, J = 4.1 Hz), 126.78, 124.25 (q, J = 271.5 Hz), 123.30 (q, J = 32.9 Hz), 115.72, 81.20, 79.77, 73.97, 58.46, 31.11, 28.28, 18.97, 16.93, 14.69. ¹⁹F NMR (471 MHz, CDCl₃) δ-61.67. 15 ESIMS m/z 418 ¹H NMR (500 MHz, CDCl₃) δ 7.40-7.25 ([M + H]⁺) (m, 5H), 7.11 (td, J = 8.3, 6.8 Hz, 1H), 6.64-6.51 (m, 3H), 5.25 (qd, J = 6.4, 4.8 Hz, 1H), 5.16 (d, J = 4.9 Hz, 1H), 4.95 (d, J = 8.2 Hz, 1H), 4.28-4.21 (m, 1H), 1.42 (s, 9H), 1.36 (d, J = 6.4 Hz, 3H), 1.14 (d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.71, 163.39 (d, J = 245.6 Hz), 159.11 (d, J = 10.8 Hz), 155.00, 136.93, 130.13 (d, J = 10.0 Hz), 128.64, 128.37, 126.87, 111.57 (d, J = 2.9 Hz), 108.08 (d, J = 21.3 Hz), 103.73 (d, J = 24.8 Hz), 81.50, 79.80, 73.93, 49.25, 28.30, 18.44, 14.91. 16 ESIMS m/z 495 ¹H NMR (500 MHz, CDCl₃) δ 7.40-7.26 ([M + H]⁺) (m, 5H), 7.19-7.08 (m, 4H), 6.97-6.92 (m, 2H), 6.65-6.50 (m, 3H), 5.17 (qd, J = 6.4, 3.8 Hz, 1H), 5.12 (d, J = 4.4 Hz, 1H), 4.88 (d, J = 8.5 Hz, 1H), 4.59-4.51 (m, 1H), 2.97 (dd, J = 13.9, 5.8 Hz, 1H), 2.90 (dd, J = 13.9, 5.9 Hz, 1H), 1.40 (s, 9H), 1.34 (d, J = 6.4 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.29, 163.41 (d, J = 245.4 Hz), 158.96 (d, J = 10.9 Hz), 155.00, 136.91, 135.75, 130.14 (d, J = 10.0 Hz), 129.33, 128.73, 128.43, 126.93, 126.80, 111.63 (d, J = 2.9 Hz), 108.07 (d, J = 21.2 Hz), 103.75 (d, J = 24.9 Hz), 81.24, 79.86, 74.68, 54.31, 37.92, 28.27, 14.49. 17 ESIMS m/z 454 ([M + Na]⁺) 18 ESIMS m/z 454 ¹H NMR (400 MHz, CDCl₃) δ 7.59-7.54 ([M + H]⁺) (m, 3H), 7.51 (dd, J = 7.6, 1.2 Hz, 1H), 7.47-7.29 (m, 6H), 5.15 (p, J = 6.4 Hz, 1H), 4.96 (d, J = 7.2 Hz, 1H), 4.39 (d, J = 6.3 Hz, 1H), 4.26-4.13 (m, 1H), 3.28-3.20 (m, 2H), 1.42 (s, 9H), 1.36 (d, J = 6.3 Hz, 3H), 1.09-0.99 (m, 4H), 0.56-0.44 (m, 2H), 0.20-0.08 (m, 2H). ¹³C NMR (126 MHz, CDCl₃) δ 172.56, 154.96, 141.18, 140.86, 139.40, 128.81, 128.71, 127.41, 127.09, 126.76, 126.51, 126.33, 83.14, 79.68, 74.08, 73.85, 49.18, 30.94, 28.31, 16.04, 10.62, 3.24, 2.75. 19 (Thin film) ESIMS m/z 428 ¹H NMR (400 MHz, CDCl₃) δ 7.28 3356, 2923, ([M + Na]⁺) (dd, J = 5.1, 1.2 Hz, 1H), 7.24-7.17 2850, 1712 (m, 2H), 7.07 (dd, J = 3.5, 1.2 Hz, 1H), 6.97 (dd, J = 5.0, 3.5 Hz, 1H), 6.95-6.85 (m, 3H), 5.46-5.34 (m, 2H), 5.06 (d, J = 7.0 Hz, 1H), 4.41-4.22 (m, 1H), 1.44 (s, 9H), 1.29 (d, J = 7.2 Hz, 3H), 1.25 (d, J = 6.0 Hz, 3H). 20 (Thin film) ESIMS m/z 428 ¹H NMR (400 MHz, CDCl₃) δ 7.31-7.17 3358, 2979, ([M + Na]⁺) (m, 3H), 7.07 (dt, J = 3.4, 1.0 2929, 1712 Hz, 1H), 7.00-6.85 (m, 4H), 5.42 (d, J = 5.1 Hz, 1H), 5.39-5.31 (m, 1H), 5.06-4.93 (m, 1H), 4.40-4.21 (m, 1H), 1.43 (s, 9H), 1.39 (d, J = 6.4 Hz, 3H), 1.21 (d, J = 7.2 Hz, 3H). 21 ESIMS m/z 491 ¹H NMR (400 MHz, CDCl₃) δ 7.40-7.29 [(M + Na)⁺] (m, 6H), 6.97 (dd, J = 8.8, 2.6 Hz, 1H), 6.64 (d, J = 8.9 Hz, 1H), 5.50-5.37 (m, 1H), 5.14 (d, J = 6.8 Hz, 1H), 5.07 (d, J = 8.1 Hz, 1H), 4.37-4.24 (m, 1H), 1.44 (s, 9H), 1.29 (d, J = 7.2 Hz, 3H), 1.21 (d, J = 6.5 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 206.90, 172.67, 155.04, 151.85, 136.01, 130.07, 128.88, 128.81, 127.30, 127.18, 125.99, 124.11, 115.42, 82.78, 79.76, 73.14, 49.33, 28.33, 18.68, 16.21. 22 ESIMS m/z 401 ¹H NMR (400 MHz, CDCl₃) δ 8.66 ([M + H]⁺) (d, J = 2.2 Hz, 1H), 8.55 (dd, J = 4.8, 1.7 Hz, 1H), 7.74 (dt, J = 7.9, 2.0 Hz, 1H), 7.33-7.27 (m, 1H), 7.24-7.10 (m, 2H), 6.92 (tt, J = 7.3, 1.1 Hz, 1H), 6.87-6.74 (m, 2H), 5.32-5.24 (m, 1H), 5.21 (d, J = 5.4 Hz, 1H), 4.95 (d, J = 7.4 Hz, 1H), 4.31-4.14 (m, 1H), 1.42 (s, 9H), 1.40 (d, J = 6.3 Hz, 3H), 1.14 (d, J = 7.2 Hz, 3H). 23 (Thin film) ESIMS m/z 407 ¹H NMR (400 MHz, CDCl₃) δ 7.80 3351, 2979, ([M + H]⁺) (dd, J = 3.2, 1.3 Hz, 1H), 7.35 (t, J = 1704, 1491 3.2 Hz, 1H), 7.25-7.16 (m, 2H), 7.03-6.89 (m, 3H), 5.66-5.54 (m, 1H), 5.54-5.45 (m, 1H), 5.18-5.01 (m, 1H), 4.38-4.22 (m, 1H), 1.44 (s, 9H), 1.35 (d, J = 6.4 Hz, 3H), 1.25 (d, J = 7.8 Hz, 3H). 24 ESIMS m/z 494 ¹H NMR (400 MHz, CDCl₃) δ 7.59-7.51 ([M + H]⁺) (m, 4H), 7.46-7.40 (m, 3H), 7.35 (ddd, J = 4.9, 4.1, 2.6 Hz, 2H), 7.16-7.09 (m, 1H), 6.61 (ddt, J = 13.3, 4.6, 2.3 Hz, 3H), 5.33-5.27 (m, 2H), 5.23 (d, J = 4.9 Hz, 1H), 4.95 (d, J = 7.2 Hz, 1H), 4.30-4.20 (m, 1H), 1.42 (s, 9H), 1.40 (d, J = 6.4 Hz, 3H), 1.11 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 164.64, 141.66, 140.57, 137.60, 130.24, 129.12, 128.84, 127.58, 127.20, 127.14, 125.75, 125.53, 111.62, 108.30, 108.09, 103.94, 103.69, 99.99, 81.63, 74.01, 60.39, 28.29, 18.39, 14.90, 14.20. 25 ESIMS m/z 380.6 ¹H NMR (400 MHz, CDCl₃) δ 7.38-7.27 ([M + H]⁺) (m, 5H), 5.26-4.89 (m, 2H), 4.39-4.26 (m, 1H), 4.22 (d, J = 6.8 Hz, 1H), 3.15-2.97 (m, 2H), 1.92-1.74 (m, 1H), 1.44 (s, 9H), 1.35 (dd, J = 7.0, 2.6 Hz, 3H), 1.06 (d, J = 6.5 Hz, 3H), 0.86 (d, J = 6.7 Hz, 6H). 26 ESIMS m/z 380.6 ¹H NMR (400 MHz, CDCl₃) δ 7.37-7.27 ([M + H]⁺) (m, 5H), 5.11-5.03 (m, 1H), 4.97 (d, J = 7.9 Hz, 1H), 4.22 (d, J = 6.1 Hz, 1H), 4.18 (d, J = 8.1 Hz, 1H), 3.14 (dd, J = 8.8, 6.5 Hz, 1H), 3.04 (dd, J = 8.8, 6.4 Hz, 1H), 1.92-1.76 (m, 1H), 1.43 (s, 9H), 1.30 (d, J = 6.3 Hz, 3H), 1.06 (d, J = 7.2 Hz, 3H), 0.90 (d, J = 3.9 Hz, 3H), 0.88 (d, J = 3.9 Hz, 3H). 27 ESIMS m/z 388 ¹H NMR (400 MHz, CDCl₃) δ 7.39-7.27 ([M + Na]⁺) (m, 5H), 5.22-5.10 (m, 1H), 5.09 (d, J = 7.8 Hz, 1H), 4.40-4.27 (m, 1H), 4.22 (d, J = 6.9 Hz, 1H), 3.36-3.16 (m, 2H), 1.60-1.48 (m, 2H), 1.44 (s, 9H), 1.35 (d, J = 7.1 Hz, 3H), 1.06 (d, J = 6.5 Hz, 3H), 0.87 (t, J = 7.4 Hz, 3H). 28 ESIMS m/z 388 ¹H NMR (400 MHz, CDCl₃) δ 7.39-7.27 ([M + Na]⁺) (m, 5H), 5.18-5.02 (m, 1H), 4.98 (d, J = 8.0 Hz, 1H), 4.24 (d, J = 6.1 Hz, 1H), 4.23-4.12 (m, 1H), 3.33 (dt, J = 9.1, 6.6 Hz, 1H), 3.25 (dt, J = 9.1, 6.4 Hz, 1H), 1.57 (dtd, J = 13.8, 7.4, 6.5 Hz, 2H), 1.43 (s, 9H), 1.29 (d, J = 6.4 Hz, 3H), 1.06 (d, J = 7.2 Hz, 3H), 0.90 (t, J = 7.4 Hz, 3H). 29 ESIMS m/z 360 ¹H NMR (400 MHz, CDCl₃) δ 7.41-7.28 ([M + Na]⁺) (m, 5H), 5.24-5.12 (m, 1H), 5.08 (d, J = 5.5 Hz, 1H), 4.40-4.24 (m, 1H), 4.11 (d, J = 6.9 Hz, 1H), 3.90 (s, 3H), 1.44 (s, 9H), 1.36 (d, J = 7.0 Hz, 3H), 1.07 (d, J = 6.5 Hz, 3H). 30 ESIMS m/z 360 ¹H NMR (400 MHz, CDCl₃) δ 7.38-7.28 ([M + Na]⁺) (m, 5H), 5.16-5.05 (m, 1H), 4.97 (d, J = 7.7 Hz, 1H), 4.31-4.18 (m, 1H), 4.17 (d, J = 5.9 Hz, 1H), 3.26 (s, 3H), 1.43 (s, 9H), 1.28 (d, J = 6.4 Hz, 3H), 1.08 (d, J = 7.2 Hz, 3H). 31 ESIMS m/z 400 ¹H NMR (400 MHz, CDCl₃) δ 7.36-7.28 ([M + Na]⁺) (m, 5H), 5.22-5.11 (m, 1H), 5.10 (d, J = 5.1 Hz, 1H), 4.37-4.27 (m, 2H), 3.90 (s, 3H), 3.21-3.08 (m, 2H), 1.44 (s, 9H), 1.37 (d, J = 7.1 Hz, 3H), 1.08 (d, J = 6.5 Hz, 3H), 1.01-0.94 (m, 1H), 0.54-0.39 (m, 2H), 0.17-0.02 (m, 2H). 32 ESIMS m/z 476 ¹H NMR (400 MHz, CDCl₃) δ 7.62 ([M + H]⁺) (s, 1H), 7.55 (d, J = 7.4 Hz, 2H), 7.51 (dd, J = 7.0, 1.7 Hz, 1H), 7.46-7.32 (m, 5H), 7.19 (dd, J = 8.2, 7.6 Hz, 2H), 6.88 (dd, J = 13.9, 7.9 Hz, 3H), 5.34-5.28 (m, 1H), 5.25 (d, J = 5.0 Hz, 1H), 4.96 (d, J = 7.3 Hz, 1H), 4.29-4.17 (m, 1H), 1.44-1.39 (m, 12H), 1.09 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.80, 157.95, 154.98, 141.49, 140.68, 138.25, 129.41, 129.01, 128.81, 127.50, 127.13, 126.97, 125.86, 125.65, 121.29, 116.04, 81.38, 74.23, 49.24, 28.30, 18.39, 15.03. 33 ESIMS m/z 498 ¹H NMR (400 MHz, CDCl₃) δ 7.58-7.54 ([M + Na]⁺) (m, 4H), 7.48-7.40 (m, 4H), 7.36-7.31 (m, 1H), 7.23-7.17 (m, 2H), 6.93-6.84 (m, 3H), 5.29 (p, J = 6.3 Hz, 1H), 5.23 (d, J = 4.9 Hz, 1H), 4.96 (d, J = 7.1 Hz, 1H), 4.31-4.20 (m, 1H), 1.42 (s, 9H), 1.40 (d, J = 6.4 Hz, 3H), 1.14 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.77, 157.90, 141.05, 140.53, 136.56, 129.40, 128.77, 127.42, 127.39, 127.24, 127.04, 121.25, 116.00, 81.03, 74.17, 49.29, 28.30, 18.47, 15.03. 34 ESIMS m/z 418 ¹H NMR (400 MHz, CDCl₃) δ 7.40-7.34 ([M + H]⁺) (m, 2H), 7.22-7.15 (m, 2H), 7.02 (dd, J = 14.6, 5.9 Hz, 2H), 6.90 (t, J = 7.4 Hz, 1H), 6.83-6.78 (m, 2H), 5.26-5.19 (m, 1H), 5.15 (d, J = 5.1 Hz, 1H), 4.94 (d, J = 7.2 Hz, 1H), 4.24 (dt, J = 13.4, 6.8 Hz, 1H), 1.42 (s, 9H), 1.37 (d, J = 6.4 Hz, 3H), 1.13 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-113.75 (s, 1F). 35 ESIMS m/z 419 ¹H NMR (400 MHz, CDCl₃) δ 7.39-7.27 ([M + H]⁺) (m, 5H), 6.90-6.81 (m, 2H), 6.81-6.68 (m, 2H), 5.24 (qd, J = 6.4, 4.8 Hz, 1H), 5.09 (d, J = 4.9 Hz, 1H), 5.00-4.89 (m, 1H), 4.32-4.16 (m, 1H), 1.42 (s, 9H), 1.36 (d, J = 6.5 Hz, 3H), 1.12 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-123.15. 36 ESIMS m/z 437 ¹H NMR (400 MHz, CDCl₃) δ 7.39-7.29 ([M + H]⁺) (m, 2H), 7.11-6.98 (m, 2H), 6.92-6.81 (m, 2H), 6.79-6.68 (m, 2H), 5.39-5.27 (m, 1H), 5.05-4.98 (m, 2H), 4.38-4.25 (m, 1H), 1.44 (s, 9H), 1.27 (d, J = 7.3 Hz, 3H), 1.19 (d, J = 6.5 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-113.06, −122.98. 37 ESIMS m/z 449 ¹H NMR (300 MHz, CDCl₃) δ 7.44-7.27 ([M + H]⁺) (m, 5H), 7.19-7.12 (m, 1H), 6.78 (ddd, J = 8.4, 2.2, 0.8 Hz, 1H), 6.54 (d, J = 8.4 Hz, 1H), 5.35-5.27 (m, 1H), 5.20 (d, J = 4.8 Hz, 1H), 4.97 (d, J = 7.2 Hz, 1H), 4.37-4.15 (m, 1H), 2.19 (s, 3H), 1.46-1.32 (m, 12H), 1.15 (d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.71, 151.07, 137.00, 131.53, 130.75, 128.57, 128.54, 128.31, 127.84, 126.97, 123.12, 115.12, 82.12, 79.73, 74.17, 28.30, 20.24, 18.45. 38 ESIMS m/z 467 ¹H NMR (300 MHz, CDCl₃) δ 7.44-7.32 ([M + H]⁺) (m, 2H), 7.15 (dd, J = 2.2, 0.8 Hz, 1H), 7.10-6.96 (m, 2H), 6.80 (ddd, J = 8.5, 2.1, 0.8 Hz, 1H), 6.53 (d, J = 8.4 Hz, 1H), 5.27 (qd, J = 6.4, 4.8 Hz, 1H), 5.18 (d, J = 4.9 Hz, 1H), 4.96 (d, J = 8.2 Hz, 1H), 4.36-4.12 (m, 1H), 2.20 (s, 3H), 1.42 (s, 9H), 1.41 (d, J = 8.0 Hz, 3H), 1.16 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (471 MHz, CDCl₃) δ-113.45. 39 ESIMS m/z 436 ¹H NMR (400 MHz, CDCl₃) δ 7.43 ([M + H]⁺) (td, J = 8.7, 6.5 Hz, 1H), 7.25-7.16 (m, 2H), 6.95-6.89 (m, 1H), 6.89-6.78 (m, 4H), 5.47 (d, J = 5.8 Hz, 1H), 5.33 (p, J = 6.1 Hz, 1H), 4.97 (d, J = 7.2 Hz, 1H), 4.32-4.18 (m, 1H), 1.43 (s, 9H), 1.39 (d, J = 6.4 Hz, 3H), 1.17 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (471 MHz, CDCl₃) δ-109.59 (d, J = 6.7 Hz), −113.96 (s). 40 ESIMS m/z 414 ¹H NMR (400 MHz, CDCl₃) δ 7.27 ([M + H]⁺) (d, J = 6.8 Hz, 3H), 7.19-7.11 (m, 4H), 6.87 (t, J = 7.4 Hz, 1H), 6.82 (d, J = 7.8 Hz, 2H), 5.28-5.21 (m, 1H), 5.15 (d, J = 4.8 Hz, 1H), 4.96 (d, J = 7.2 Hz, 1H), 4.29-4.19 (m, 1H), 2.31 (s, 3H), 1.42 (s, 9H), 1.35 (d, J = 6.4 Hz, 3H), 1.14 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.73, 157.95, 137.83, 134.48, 129.33, 129.19, 126.87, 121.09, 115.96, 81.07, 74.22, 28.31, 21.15, 18.51, 14.93. 41 ESIMS m/z 452 ¹H NMR (400 MHz, CDCl₃) δ 7.37 ([M + Na]⁺). (d, J = 7.6 Hz, 1H), 7.26-7.21 (m, 1H), 7.16 (t, J = 7.8 Hz, 2H), 6.86 (dt, J = 18.3, 8.1 Hz, 5H), 5.66 (d, J = 4.6 Hz, 1H), 5.39-5.31 (m, 1H), 5.01 (s, 1H), 4.25 (s, 1H), 3.91 (s, 3H), 1.42 (s, 9H), 1.33 (d, J = 6.5 Hz, 3H), 1.17 (d, J = 7.2 Hz, 3H). ¹³C NMR (376 MHz, CDCl₃) δ 172.50, 157.92, 156.64, 154.95, 129.29, 129.11, 127.82, 125.54, 120.89, 120.85, 115.65, 110.22, 79.63, 74.92, 73.02, 55.48, 49.36, 28.32, 18.60, 15.02. 42 ESIMS m/z 470 ¹H NMR (400 MHz, CDCl₃) δ 7.33 ([M + Na]⁺) (t, J = 7.7 Hz, 1H), 7.17 (t, J = 7.9 Hz, 2H), 6.87 (t, J = 7.3 Hz, 1H), 6.80 (d, J = 8.2 Hz, 2H), 6.60 (dd, J = 13.0, 5.7 Hz, 2H), 5.58 (d, J = 4.7 Hz, 1H), 5.33 (dd, J = 11.9, 5.7 Hz, 1H), 4.99 (s, 1H), 4.25 (s, 1H), 3.90 (s, 3H), 1.42 (s, 9H), 1.32 (d, J = 6.5 Hz, 3H), 1.18 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.46, 163.39 (d, J = 246.4 Hz), 157.82 (d, J = 9.7 Hz), 157.68, 154.95, 129.34, 128.98 (d, J = 10.1 Hz), 121.31 (d, J = 3.2 Hz), 121.07, 115.60, 107.38 (d, J = 21.3 Hz), 98.70 (d, J = 25.8 Hz), 79.70, 74.55, 72.89, 55.78, 49.36, 28.31, 18.59, 15.08. ¹⁹F NMR (376 MHz, CDCl₃) δ-111.26 (s, 1F). 43 ESIMS m/z 462 ¹H NMR (400 MHz, CDCl₃) δ 7.27 ([M + H]⁺) (d, J = 6.6 Hz, 2H), 7.19-7.08 (m, 3H), 6.78 (ddd, J = 8.6, 2.1, 0.9 Hz, 1H), 6.54 (d, J = 8.4 Hz, 1H), 5.33-5.23 (m, 1H), 5.17 (d, J = 4.6 Hz, 1H), 4.98 (d, J = 8.0 Hz, 1H), 4.37-4.15 (m, 1H), 2.31 (s, 3H), 2.19 (s, 3H), 1.42 (s, 9H), 1.39 (d, J = 6.5 Hz, 3H), 1.17 (d, J = 7.2 Hz, 3H). 44 ESIMS m/z 432 ¹H NMR (400 MHz, CDCl₃) δ 7.28-7.21 ([M + H]⁺) (m, 2H), 7.14 (d, J = 7.8 Hz, 2H), 6.89-6.80 (m, 2H), 6.80-6.72 (m, 2H), 5.23 (qd, J = 6.4, 4.7 Hz, 1H), 5.06 (d, J = 4.8 Hz, 1H), 5.02-4.92 (m, 1H), 4.33-4.17 (m, 1H), 2.31 (s, 3H), 1.42 (s, 9H), 1.35 (d, J = 6.4 Hz, 3H), 1.15 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-123.28. 45 ESIMS m/z 436 ¹H NMR (400 MHz, CDCl₃) δ 7.41-7.30 ([M + H]⁺) (m, 2H), 7.09-6.97 (m, 2H), 6.90-6.81 (m, 2H), 6.80-6.66 (m, 2H), 5.22 (qd, J = 6.4, 4.9 Hz, 1H), 5.08 (d, J = 5.1 Hz, 1H), 5.04-4.91 (m, 1H), 4.31-4.18 (m, 1H), 1.42 (s, 9H), 1.36 (d, J = 6.4 Hz, 3H), 1.14 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-113.44, −122.75. 46 ESIMS m/z 430 ¹H NMR (400 MHz, CDCl₃) δ 7.24 ([M + H]⁺) (t, J = 7.9 Hz, 1H), 7.20-7.15 (m, 2H), 6.98 (d, J = 7.6 Hz, 1H), 6.94-6.92 (m, 1H), 6.89 (t, J = 7.4 Hz, 1H), 6.85-6.78 (m, 3H), 5.28-5.21 (m, 1H), 5.15 (d, J = 4.9 Hz, 1H), 4.97 (d, J = 5.5 Hz, 1H), 4.31-4.17 (m, 1H), 3.77 (s, 3H), 1.42 (s, 9H), 1.37 (d, J = 6.4 Hz, 3H), 1.14 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.72, 159.79, 157.98, 154.99, 139.27, 129.54, 129.35, 121.23, 119.32, 115.98, 113.49, 112.51, 81.16, 79.76, 74.18, 55.20, 49.30, 28.30, 18.44, 14.92. 47 ESIMS m/z 432 ¹H NMR (400 MHz, CDCl₃) δ 7.36 ([M + H]⁺) (dd, J = 8.6, 5.9 Hz, 1H), 7.20-7.15 (m, 2H), 6.85 (ddd, J = 12.0, 11.1, 5.0 Hz, 3H), 6.76-6.71 (m, 2H), 5.36 (d, J = 5.0 Hz, 1H), 5.21-5.13 (m, 1H), 4.93 (d, J = 7.0 Hz, 1H), 4.24 (s, 1H), 2.50 (s, 3H), 1.43-1.39 (m, 12H), 1.09 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (101 MHz, CDCl₃) δ-114.88 (s, 1F). 48 ESIMS m/z 474 ¹H NMR (400 MHz, CDCl₃) δ 7.48 ([M + Na]⁺) (dd, J = 8.8, 6.1 Hz, 1H), 7.24-7.17 (m, 2H), 7.13 (dd, J = 8.4, 2.6 Hz, 1H), 6.94 (ddd, J = 18.0, 11.6, 4.9 Hz, 2H), 6.82-6.77 (m, 2H), 5.61 (d, J = 5.4 Hz, 1H), 5.35-5.28 (m, 1H), 4.97 (d, J = 5.8 Hz, 1H), 4.32-4.21 (m, 1H), 1.42 (s, 9H), 1.39 (d, J = 6.4 Hz, 3H), 1.17 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-111.26 (s, 1F). 49 ESIMS m/z 432 ¹H NMR (400 MHz, CDCl₃) δ 7.30 ([M + H]⁺) (t, J = 7.7 Hz, 1H), 7.22-7.16 (m, 2H), 6.92-6.81 (m, 5H), 5.48 (d, J = 5.6 Hz, 1H), 5.34 (p, J = 6.3 Hz, 1H), 4.99 (d, J = 6.4 Hz, 1H), 4.31-4.18 (m, 1H), 2.30 (s, 3H), 1.42 (s, 9H), 1.38 (d, J = 6.4 Hz, 3H), 1.16 (d, J = 7.1 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-119.17 (s, 1F). 50 ESIMS m/z 450 ¹H NMR (400 MHz, CDCl₃) δ 8.40 ([M + H]⁺) (d, J = 8.5 Hz, 1H), 7.89 (d, J = 8.1 Hz, 1H), 7.79 (d, J = 8.2 Hz, 1H), 7.64 (t, J = 8.0 Hz, 2H), 7.54 (t, J = 7.5 Hz, 1H), 7.44-7.38 (m, 1H), 7.12 (dd, J = 8.5, 7.5 Hz, 2H), 6.85 (t, J = 7.3 Hz, 1H), 6.79 (d, J = 8.5 Hz, 2H), 6.07 (d, J = 4.0 Hz, 1H), 5.46-5.39 (m, 1H), 4.96 (d, J = 5.1 Hz, 1H), 4.31-4.18 (m, 1H), 1.44-1.38 (m, 12H), 1.00 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 173.23, 158.01, 155.02, 133.75, 133.03, 130.60, 129.39, 129.02, 128.66, 126.78, 125.85, 125.47, 124.72, 122.88, 121.13, 115.68, 79.78, 77.52, 73.84, 49.25, 28.31, 18.25, 14.36. 51 ESIMS m/z 467 ¹H NMR (400 MHz, CDCl₃) δ 7.87-7.77 ([M + NH₄]⁺) (m, 4H), 7.53 (dd, J = 8.5, 1.6 Hz, 1H), 7.50-7.44 (m, 2H), 7.16 (dd, J = 9.6, 6.5 Hz, 2H), 6.90-6.84 (m, 3H), 5.40-5.31 (m, 2H), 4.94 (d, J = 5.8 Hz, 1H), 4.31-4.18 (m, 1H), 1.43-1.38 (m, 12H), 1.09 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.74, 157.99, 154.99, 135.15, 133.18, 133.10, 129.38, 128.44, 127.94, 127.73, 126.32, 126.28, 126.20, 124.37, 121.28, 116.07, 81.46, 79.77, 74.22, 49.27, 28.30, 18.43, 14.95. 52 ESIMS m/z 491 ¹H NMR (400 MHz, CDCl₃) δ 7.34 ([M + NH₄]⁺) (dd, J = 9.2, 6.1 Hz, 1H), 7.21-7.15 (m, 2H), 6.88 (t, J = 7.4 Hz, 1H), 6.81 (d, J = 7.9 Hz, 2H), 6.61 (ddd, J = 10.9, 5.1, 2.4 Hz, 2H), 6.09 (ddt, J = 17.2, 10.4, 5.1 Hz, 1H), 5.63 (d, J = 4.6 Hz, 1H), 5.47 (ddd, J = 17.3, 3.0, 1.5 Hz, 1H), 5.39-5.31 (m, 2H), 5.02 (d, J = 6.1 Hz, 1H), 4.67-4.56 (m, 2H), 4.32-4.19 (m, 1H), 1.42 (s, 9H), 1.32 (d, J = 6.5 Hz, 3H), 1.19 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-111.28 (s, 1F). 53 ESIMS m/z 504 ¹H NMR (400 MHz, CDCl₃) δ 7.34 ([M + Na]⁺) (ddd, J = 9.5, 8.5, 4.1 Hz, 2H), 7.05-7.00 (m, 1H), 6.82 (td, J = 7.7, 1.3 Hz, 1H), 6.67-6.60 (m, 3H), 5.66 (d, J = 4.4 Hz, 1H), 5.41-5.32 (m, 1H), 5.01 (d, J = 6.6 Hz, 1H), 4.33-4.21 (m, 1H), 3.90 (s, 3H), 1.42 (s, 9H), 1.36 (d, J = 6.5 Hz, 3H), 1.22 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-110.78 (s). 54 ESIMS m/z 484 ¹H NMR (400 MHz, CDCl₃) δ 7.35-7.29 ([M + Na]⁺) (m, 1H), 7.21-7.14 (m, 2H), 6.88 (t, J = 7.3 Hz, 1H), 6.81 (d, J = 7.9 Hz, 2H), 6.62-6.55 (m, 2H), 5.60 (d, J = 4.4 Hz, 1H), 5.39-5.31 (m, 1H), 5.03 (d, J = 5.3 Hz, 1H), 4.33-4.20 (m, 1H), 4.10 (q, J = 7.0 Hz, 2H), 1.49 (t, J = 7.0 Hz, 3H), 1.42 (s, 9H), 1.31 (d, J = 6.5 Hz, 3H), 1.20 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-111.52 (s, 1F). 56 ESIMS m/z 461 ¹H NMR (400 MHz, CDCl₃) δ 7.23 ([M + NH₄]⁺) (d, J = 7.6 Hz, 1H), 7.19-7.13 (m, 2H), 6.88-6.79 (m, 3H), 6.70 (d, J = 7.8 Hz, 2H), 5.61 (d, J = 4.5 Hz, 1H), 5.37-5.30 (m, 1H), 5.04 (d, J = 5.9 Hz, 1H), 4.32-4.20 (m, 1H), 3.89 (s, 3H), 2.31 (s, 3H), 1.42 (s, 9H), 1.31 (d, J = 6.5 Hz, 3H), 1.19 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.50, 157.97, 156.56, 154.98, 139.18, 129.26, 127.66, 122.44, 121.53, 120.79, 115.64, 111.13, 79.64, 74.88, 73.09, 55.42, 49.39, 28.33, 21.56, 18.64, 14.97. 57 ESIMS m/z 518 ¹H NMR (400 MHz, CDCl₃) δ 7.36 ([M + Na]⁺) (dd, J = 8.7, 6.7 Hz, 1H), 7.14 (d, J = 1.7 Hz, 1H), 6.81 (dd, J = 8.4, 1.6 Hz, 1H), 6.63 (dd, J = 12.8, 5.8 Hz, 2H), 6.54 (d, J = 8.4 Hz, 1H), 5.61 (d, J = 4.4 Hz, 1H), 5.39-5.32 (m, 1H), 5.02 (d, J = 6.1 Hz, 1H), 4.32-4.19 (m, 1H), 3.89 (s, 3H), 2.20 (s, 3H), 1.42 (s, 9H), 1.35 (d, J = 6.5 Hz, 3H), 1.22 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-110.94 (s). 58 ESIMS m/z 514 ¹H NMR (400 MHz, CDCl₃) δ 7.26 ([M + Na]⁺) (d, J = 7.7 Hz, 1H), 7.12 (d, J = 1.8 Hz, 1H), 6.79 (dd, J = 8.4, 1.6 Hz, 1H), 6.72 (d, J = 7.9 Hz, 1H), 6.69 (s, 1H), 6.56 (d, J = 8.4 Hz, 1H), 5.63 (d, J = 4.2 Hz, 1H), 5.37 (qd, J = 6.5, 4.4 Hz, 1H), 5.05 (d, J = 7.1 Hz, 1H), 4.32-4.20 (m, 1H), 3.88 (s, 3H), 2.31 (s, 3H), 2.18 (s, 3H), 1.42 (s, 9H), 1.35 (d, J = 6.5 Hz, 3H), 1.22 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.46, 156.52, 154.99, 151.15, 139.39, 130.93, 130.58, 127.85, 127.70, 122.80, 121.86, 121.61, 114.38, 111.08, 79.60, 75.69, 73.10, 55.41, 49.41, 28.31, 21.58, 20.20, 18.65, 14.85. 59 ESIMS m/z 510 ¹H NMR (400 MHz, CDCl₃) δ 7.35-7.30 ([M + Na]⁺) (m, 1H), 7.21-7.16 (m, 2H), 6.88 (t, J = 7.3 Hz, 1H), 6.83 (d, J = 7.8 Hz, 2H), 6.62-6.54 (m, 2H), 5.63 (d, J = 4.7 Hz, 1H), 5.39-5.32 (m, 1H), 5.02 (d, J = 8.5 Hz, 1H), 4.31-4.21 (m, 1H), 3.89 (d, J = 6.8 Hz, 2H), 1.42 (s, 9H), 1.36-1.27 (m, 4H), 1.21 (d, J = 7.2 Hz, 3H), 0.71-0.65 (m, 2H), 0.40 (q, J = 4.6 Hz, 2H). ¹⁹F NMR (376 MHz, CDCl₃) δ-111.48 (s). 60 ESIMS m/z 498 ¹H NMR (400 MHz, CDCl₃) δ 7.37 ([M + H]⁺) (dd, J = 8.6, 6.6 Hz, 1H), 7.22-7.15 (m, 2H), 6.89 (t, J = 7.4 Hz, 1H), 6.82-6.77 (m, 2H), 6.69 (td, J = 8.3, 2.3 Hz, 1H), 6.59 (dd, J = 10.2, 2.3 Hz, 1H), 6.24 (tt, J = 54.8, 4.0 Hz, 1H), 5.59 (d, J = 4.3 Hz, 1H), 5.35-5.29 (m, 1H), 5.00 (d, J = 6.3 Hz, 1H), 4.34-4.18 (m, 3H), 1.42 (s, 9H), 1.32 (d, J = 6.5 Hz, 3H), 1.19 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-110.58 (s), −124.95 (d, J = 296.8 Hz), −125.95 (d, J = 296.7 Hz). 61 ESIMS m/z 566 ¹H NMR (400 MHz, CDCl₃) δ 7.53 ([M + Na]⁺) (dd, J = 8.7, 6.5 Hz, 1H), 7.45-7.39 (m, 2H), 7.33 (dd, J = 7.9, 1.6 Hz, 1H), 7.22 (t, J = 7.4 Hz, 1H), 7.09-7.01 (m, 3H), 6.85 (td, J = 7.7, 1.2 Hz, 1H), 6.76 (dd, J = 13.8, 5.4 Hz, 2H), 6.50 (dd, J = 10.1, 2.4 Hz, 1H), 5.78 (d, J = 4.6 Hz, 1H), 5.53-5.46 (m, 1H), 5.05 (d, J = 6.2 Hz, 1H), 4.36-4.22 (m, 1H), 1.43 (d, J = 6.6 Hz, 3H), 1.42 (s, 9H), 1.25 (d, J = 6.8 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-110.21 (s). 62 ESIMS m/z 278 ([M + H]⁺) 63 ESIMS m/z 301 ([M + H]⁺) 64 ESIMS m/z 300 ([M + H]⁺) 65 ESIMS m/z 300 ([M + H]⁺) 66 ESIMS m/z 334 ([M + H]⁺) 67 ESIMS m/z 334 ([M + H]⁺) 68 ESIMS m/z 334 ([M + H]⁺) 69 ESIMS m/z 368 ([M + H]⁺) 70 ESIMS m/z 336 ([M + H]⁺) 71 ESIMS m/z 352 ([M + H]⁺) 72 ESIMS m/z 350 ([M + H]⁺) 73 ESIMS m/z 366 ([M + H]⁺) 74 ESIMS m/z 368 ([M + H]⁺) 75 ESIMS m/z 396 ([M + H]⁺) 76 ESIMS m/z 318 ([M + H]⁺) 77 ESIMS m/z 394 ([M + H]⁺) 78 ESIMS m/z 354 ([M + H]⁺) 79 ESIMS m/z 354 ([M + H]⁺) 80 ESIMS m/z 368 ([M + H]⁺) 81 ESIMS m/z 394 ([M + H]⁺) 82 ESIMS m/z 280 ([M + H]⁺) 83 ESIMS m/z 280 ([M + H]⁺) 84 ESIMS m/z 376 ([M + H]⁺) 85 ESIMS m/z 376 ([M + H]⁺) 86 ESIMS m/z 319 ([M + H]⁺) 87 ESIMS m/z 337 ([M + H]⁺) 88 ESIMS m/z 348 ([M + H]⁺) 89 ESIMS m/z 366 ([M + H]⁺) 90 ESIMS m/z 318 ([M + H]⁺) 91 ESIMS m/z 336 ([M + H]⁺) 92 ESIMS m/z 314 ([M + H]⁺) 93 ESIMS m/z 330 ([M + H]⁺) 94 ESIMS m/z 348 ([M + H]⁺) 95 ESIMS m/z 362 ([M + H]⁺) 96 ESIMS m/z 332 ([M + H]⁺) 97 ESIMS m/z 336 ([M + H]⁺) 98 ESIMS m/z 330 ([M + H]⁺) 99 ESIMS m/z 332 ([M + H]⁺) 100 ESIMS m/z 352 ([M + H]⁺) 101 ESIMS m/z 332 ([M + H]⁺) 102 ESIMS m/z 350 ([M + H]⁺) 103 ESIMS m/z 350 ([M + H]⁺) 104 ESIMS m/z 374 ([M + H]⁺) 105 ESIMS m/z 382 ([M + H]⁺) 106 ESIMS m/z 362 ([M + H]⁺) 107 ESIMS m/z 344 ([M + H]⁺) 108 ESIMS m/z 396 ([M + H]⁺) 109 ESIMS m/z 392 ([M + H]⁺) 110 ESIMS m/z 388 ([M + H]⁺) 111 ESIMS m/z 398 ([M + H]⁺) 112 ESIMS m/z 444 ([M + H]⁺) 113 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 12.12 [M]⁺ calcd for (d, J = 0.6 Hz, 1H), 8.40 (d, J = 8.1 C₂₃H₂₈N₂O₆, Hz, 1H), 7.97 (d, J = 5.2 Hz, 1H), 428.1947; found, 7.36-7.19 (m, 5H), 6.86 (d, J = 5.2 428.1953 Hz, 1H), 5.14 (h, J = 6.3 Hz, 1H), 4.66-4.52 (m, 1H), 4.33 (d, J = 6.4 Hz, 1H), 3.94 (s, 3H), 3.26-3.12 (m, 2H), 1.35 (d, J = 6.3 Hz, 3H), 1.22 (d, J = 7.2 Hz, 3H), 1.01 (ttt, J = 8.1, 6.7, 4.8 Hz, 1H), 0.54-0.40 (m, 2H), 0.19-0.04 (m, 2H). 114 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 12.08 [M]⁺ calcd for (s, 1H), 8.40 (d, J = 7.9 Hz, 1H), C₂₅H₂₆N₂O₆, 7.97 (d, J = 5.2 Hz, 1H), 7.42-7.34 450.1791; found, (m, 2H), 7.35-7.20 (m, 3H), 7.21-7.08 450.1795 (m, 2H), 6.91-6.75 (m, 4H), 5.30 (qd, J = 6.5, 5.2 Hz, 1H), 5.20 (d, J = 5.1 Hz, 1H), 4.64 (p, J = 7.3 Hz, 1H), 3.93 (s, 3H), 1.40 (d, J = 6.4 Hz, 3H), 1.30 (d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.55, 168.65, 157.83, 155.34, 148.72, 140.44, 137.48, 130.40, 129.34, 128.53, 128.19, 126.95, 121.19, 115.92, 109.42, 81.18, 74.52, 56.06, 47.93, 18.02, 15.09. 115 (Thin film) HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.12 3367.32, 2984.27, ([M + H]⁺) calcd for (d, J = 0.6 Hz, 1H), 8.39 (d, J = 7.9 1737.93, 1648.90, C₂₅H₂₇N₂O₆, Hz, 1H), 7.99 (d, J = 5.2 Hz, 1H), 1527.87, 1480.95, 451.1864; found, 7.42-7.37 (m, 2H), 7.35-7.28 (m, 1237.99 451.1869 2H), 7.20-7.11 (m, 2H), 6.90-6.80 (m, 5H), 5.32-5.22 (m, 2H), 4.73-4.49 (m, 1H), 3.95 (s, 3H), 1.45 (d, J = 7.2 Hz, 3H), 1.37 (d, J = 6.3 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.45, 168.64, 157.85, 155.38, 148.76, 140.45, 137.46, 130.48, 129.35, 128.54, 128.12, 126.83, 121.22, 116.05, 109.44, 81.10, 74.75, 56.08, 47.92, 18.13, 14.56. 116 (Thin film) HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.08 3367.65, 2984.35, ([M + H]⁺) calcd for (d, J = 0.6 Hz, 1H), 8.40 (d, J = 7.9 1738.51, 1648.67, C₂₅H₂₇N₂O₆, Hz, 1H), 7.97 (d, J = 5.2 Hz, 1H), 1528.19, 1480.80, 451.1864; found, 7.43-7.37 (m, 2H), 7.34-7.27 (m, 1238.38 451.1872 2H), 7.20-7.11 (m, 2H), 6.93-6.78 (m, 5H), 5.30 (qd, J = 6.4, 5.1 Hz, 1H), 5.20 (d, J = 5.1 Hz, 1H), 4.69-4.58 (m, 1H), 3.94 (s, 3H), 1.40 (d, J = 6.4 Hz, 3H), 1.30 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.55, 168.66, 157.85, 155.36, 148.74, 140.44, 137.50, 130.43, 129.35, 128.54, 128.20, 126.96, 121.20, 115.94, 109.44, 81.21, 74.53, 56.06, 47.94, 18.02, 15.10. 117 (Thin film) HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.05 3368, 2939, ([M + H]⁺) calcd for (d, J = 0.6 Hz, 1H), 8.40 (d, J = 7.9 1739, 1648, C₂₅H₂₆ClN₂O₆, Hz, 1H), 7.97 (d, J = 5.2 Hz, 1H), 1577, 1528, 485.1474; found, 7.44-7.38 (m, 2H), 7.36-7.28 (m, 1480, 1446, 485.1476 4H), 7.00 (ddd, J = 8.3, 7.5, 1.7 Hz, 1242, 1059 1H), 6.89-6.77 (m, 2H), 6.66 (dd, J = 8.3, 1.4 Hz, 1H), 5.40-5.30 (m, 1H), 5.28 (d, J = 4.7 Hz, 1H), 4.70-4.59 (m, 1H), 3.94 (s, 3H), 1.45 (d, J = 6.4 Hz, 3H), 1.34 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.59, 168.69, 155.34, 153.24, 148.72, 140.45, 136.73, 130.41, 130.30, 128.63, 128.43, 127.44, 126.89, 123.48, 121.77, 115.06, 109.43, 81.93, 74.57, 56.06, 47.97, 17.97, 14.86. 118 (Thin film) HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.04 3368, 2939, ([M + H]⁺) calcd for (d, J = 0.6 Hz, 1H), 8.39 (d, J = 7.9 1739, 1648, C₂₅H₂₆ClN₂O₆, Hz, 1H), 7.96 (d, J = 5.2 Hz, 1H), 1576, 1528, 485.1474; found, 7.38-7.27 (m, 5H), 7.11-7.02 (m, 1476, 1452, 485.1474 1H), 6.89-6.80 (m, 3H), 6.67 (ddd, 1241 J = 8.3, 2.3, 1.1 Hz, 1H), 5.35-5.24 (m, 1H), 5.19 (d, J = 4.9 Hz, 1H), 4.64 (dq, J = 8.4, 7.3 Hz, 1H), 3.93 (s, 3H), 1.38 (d, J = 6.4 Hz, 3H), 1.33 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.51, 168.71, 158.47, 155.35, 148.73, 140.47, 136.75, 134.71, 130.35, 130.15, 128.68, 128.43, 126.85, 121.46, 116.56, 113.93, 109.47, 81.40, 74.29, 56.06, 47.99, 17.98, 14.87. 119 (Thin film) HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.04 3368, 2939, ([M + H]⁺) calcd for (d, J = 0.6 Hz, 1H), 8.37 (d, J = 8.0 1739, 1649, C₂₅H₂₆ClN₂O₆, Hz, 1H), 7.96 (d, J = 5.2 Hz, 1H), 1577, 1529, 485.1474; found, 7.37-7.27 (m, 5H), 7.13-7.05 (m, 1488, 1452, 485.1465 2H), 6.89-6.82 (m, 1H), 6.76-6.69 1240 (m, 2H), 5.35-5.24 (m, 1H), 5.15 (d, J = 4.8 Hz, 1H), 4.70-4.57 (m, 1H), 3.94 (s, 3H), 1.37 (d, J = 6.4 Hz, 3H), 1.34 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.50, 168.74, 156.35, 155.37, 148.74, 140.45, 136.88, 130.33, 129.24, 128.65, 128.39, 126.86, 126.09, 117.14, 109.43, 81.55, 74.31, 56.08, 48.03, 17.95, 14.81. 120 (Thin film) HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.00 3368, 2939, ([M + H]⁺) calcd for (d, J = 0.6 Hz, 1H), 8.37 (d, J = 7.8 1739, 1648, C₂₅H₂₅Cl₂N₂O₆, Hz, 1H), 7.96 (d, J = 5.2 Hz, 1H), 1576, 1528, 519.1084; found, 7.40-7.25 (m, 6H), 6.94 (dd, J = 1478, 1452, 519.1067 8.8, 2.5 Hz, 1H), 6.89-6.82 (m, 1262, 1243, 1H), 6.55 (d, J = 8.8 Hz, 1H), 5.38-5.30 1058 (m, 1H), 5.23 (d, J = 4.5 Hz, 1H), 4.71-4.58 (m, 1H), 3.94 (s, 3H), 1.42 (d, J = 6.4 Hz, 3H), 1.37 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.51, 168.77, 155.34, 151.97, 148.72, 140.46, 136.16, 130.31, 129.97, 128.75, 128.62, 127.35, 126.80, 126.14, 124.24, 115.67, 109.42, 82.26, 74.33, 56.08, 48.08, 17.90, 14.64. 121 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.05 ([M + H]⁺) calcd for (d, J = 0.6 Hz, 1H), 8.39 (d, J = 7.9 C₂₅H₂₅F₂N₂O₆, Hz, 1H), 7.97 (d, J = 5.2 Hz, 1H), 487.1675; found, 7.43-7.27 (m, 5H), 6.96 (ddd, J = 487.1675 10.6, 8.9, 5.3 Hz, 1H), 6.86 (dd, J = 5.3, 0.7 Hz, 1H), 6.58-6.43 (m, 2H), 5.35 (qd, J = 6.4, 5.1 Hz, 1H), 5.18 (d, J = 5.1 Hz, 1H), 4.70-4.58 (m, 1H), 3.94 (s, 3H), 1.42 (d, J = 6.4 Hz, 3H), 1.32 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.48, 168.67, 158.31 (dd, J = 242.3, 2.6 Hz), 155.36, 149.45 (d, J = 239.0 Hz), 148.74, 146.17 (dd, J = 12.6, 10.5 Hz), 140.46, 136.19, 130.39, 128.71, 126.99, 116.40 (dd, J = 20.9, 10.1 Hz), 109.45, 107.72 (dd, J = 23.7, 6.9 Hz), 105.13 (dd, J = 27.3, 1.5 Hz), 83.03, 74.07, 56.07, 47.91, 17.93, 15.13. ¹⁹F NMR (376 MHz, CDCl₃) δ-116.63 (d, J = 15.0 Hz), −138.72 (d, J = 15.0 Hz). 122 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.01 ([M + H]⁺) calcd for (d, J = 0.6 Hz, 1H), 8.38 (d, J = 7.8 C₂₅H₂₅ClFN₂O₆, Hz, 1H), 7.97 (d, J = 5.2 Hz, 1H), 503.1380; found, 7.38-7.27 (m, 5H), 6.86 (dd, J = 503.1361 5.3, 0.7 Hz, 1H), 6.66-6.58 (m, 2H), 6.41 (dt, J = 10.5, 2.3 Hz, 1H), 5.29 (qd, J = 6.4, 4.7 Hz, 1H), 5.16 (d, J = 4.8 Hz, 1H), 4.70-4.58 (m, 1H), 3.94 (s, 3H), 1.36 (app dd, J = 6.8, 2.3 Hz, 6H). ¹³C NMR (101 MHz, CDCl₃) δ 171.45, 168.74, 163.09 (d, J = 248.1 Hz), 159.18 (d, J = 12.3 Hz), 155.37, 148.74, 140.47, 136.11, 135.26 (d, J = 13.4 Hz), 130.30, 128.80, 128.65, 126.76, 112.46 (d, J = 3.2 Hz), 109.48, 109.24 (d, J = 25.1 Hz), 102.15 (d, J = 25.0 Hz), 81.71, 74.04, 56.06, 48.02, 17.95, 14.76. ¹⁹F NMR (376 MHz, CDCl₃) δ-109.82. 123 (Thin film) HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 12.08 3371, 2972, ([M + H]⁺) calcd for (d, J = 0.6 Hz, 1H), 8.43 (d, J = 8.4 2939, 1739, C₂₆H₂₇F₂N₂O₆, Hz, 1H), 7.98 (d, J = 5.2 Hz, 1H), 1650, 1577, 501.1832; found, 7.42-7.36 (m, 2H), 7.36-7.28 (m, 1509, 1432, 501.1831 3H), 6.96 (ddd, J = 10.5, 9.0, 5.3 1251, 1203, Hz, 1H), 6.87 (d, J = 5.3 Hz, 1H), 1146 6.57-6.49 (m, 1H), 6.46 (ddd, J = 9.7, 6.6, 3.0 Hz, 1H), 5.34 (qd, J = 6.4, 5.0 Hz, 1H), 5.18 (d, J = 5.1 Hz, 1H), 4.62 (ddd, J = 8.4, 6.8, 5.2 Hz, 1H), 3.94 (s, 3H), 1.89-1.78 (m, 1H), 1.67 (dt, J = 14.2, 7.2 Hz, 1H), 1.42 (d, J = 6.4 Hz, 3H), 0.79 (t, J = 7.4 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 170.84, 168.86, 158.31 (dd, J = 242.4, 2.6 Hz), 155.36, 149.41 (dd, J = 242.1, 3.3 Hz), 148.71, 146.16 (dd, J = 12.5, 10.7 Hz), 140.48, 136.20, 130.43, 128.73, 128.71, 126.96, 116.37 (dd, J = 20.9, 10.0 Hz), 109.43, 107.65 (dd, J = 23.9, 6.9 Hz), 105.00 (dd, J = 27.2, 1.7 Hz), 82.95, 74.15, 56.07, 53.08, 25.36, 15.15, 9.28. 124 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 12.04 ([M + H]⁺) calcd for (d, J = 0.7 Hz, 1H), 8.41 (d, J = 8.3 C₂₆H₂₇ClFN₂O₆, Hz, 1H), 7.98 (d, J = 5.2 Hz, 1H), 517.1536; found, 7.37-7.28 (m, 5H), 6.87 (dd, J = 517.1534 5.2, 0.7 Hz, 1H), 6.65-6.58 (m, 2H), 6.40 (dt, J = 10.4, 2.3 Hz, 1H), 5.29 (qd, J = 6.4, 4.7 Hz, 1H), 5.16 (d, J = 4.7 Hz, 1H), 4.61 (ddd, J = 8.3, 6.9, 5.3 Hz, 1H), 3.94 (s, 3H), 1.92-1.80 (m, 1H), 1.71 (dt, J = 14.2, 7.2 Hz, 1H), 1.36 (d, J = 6.4 Hz, 3H), 0.83 (t, J = 7.5 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 170.82, 168.91, 163.07 (d, J = 248.1 Hz), 159.14 (d, J = 12.3 Hz), 155.36, 148.71, 140.49, 136.08, 135.24 (d, J = 13.3 Hz), 130.34, 128.81, 128.65, 126.74, 112.44 (d, J = 3.3 Hz), 109.47, 109.21 (d, J = 25.1 Hz), 102.12 (d, J = 25.0 Hz), 81.66, 74.07, 56.07, 53.21, 25.38, 14.78, 9.41. ¹⁹F NMR (471 MHz, CDCl₃) δ-109.83. 125 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 12.03 ([M + H]⁺) calcd for (d, J = 0.7 Hz, 1H), 8.37 (d, J = 7.8 C₂₆H₂₆F₃N₂O₆, Hz, 1H), 7.95 (d, J = 5.2 Hz, 1H), 519.1737; found, 7.44-7.27 (m, 7H), 6.90-6.82 (m, 519.1739 3H), 5.36-5.27 (m, 1H), 5.25 (d, J = 4.8 Hz, 1H), 4.69-4.60 (m, 1H), 3.94 (s, 3H), 1.39 (d, J = 6.4 Hz, 3H), 1.35 (d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.49, 168.74, 160.08, 155.36, 148.74, 140.45, 136.46, 130.31, 128.75, 128.53, 126.80 (q, J = 3.8 Hz), 126.80, 124.25 (q, J = 271.7 Hz), 123.29 (q, J = 32.8 Hz), 115.71, 109.44, 81.26, 74.20, 56.06, 48.02, 17.95, 14.81. ¹⁹F NMR (471 MHz, CDCl₃) δ-61.64. 126 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 12.07 ([M + H]⁺) calcd for (d, J = 0.6 Hz, 1H), 8.43 (d, J = 9.2 C₂₈H₃₀F₃N₂O₆, Hz, 1H), 7.95 (d, J = 5.2 Hz, 1H), 547.2050; found, 7.43-7.26 (m, 7H), 6.88-6.82 (m, 547.2059 3H), 5.35-5.25 (m, 2H), 4.59 (dd, J = 9.2, 4.9 Hz, 1H), 3.94 (s, 3H), 2.21-2.10 (m, 1H), 1.38 (d, J = 6.4 Hz, 3H), 0.92 (d, J = 6.9 Hz, 3H), 0.80 (d, J = 6.9 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 170.52, 169.07, 160.05, 155.37, 148.69, 140.48, 136.40, 130.39, 128.76, 128.52, 126.77 (q, J = 3.8 Hz), 126.76, 124.25 (q, J = 271.4 Hz), 123.24 (q, J = 32.7 Hz), 115.67, 109.42, 81.15, 74.25, 57.08, 56.06, 31.17, 19.11, 17.38, 14.69. ¹⁹F NMR (471 MHz, CDCl₃) δ-61.64. 127 (Thin film) HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 12.04 3369, 2940, ([M + H]⁺) calcd for (d, J = 0.6 Hz, 1H), 8.39 (d, J = 7.8 1740, 1649, C₂₅H₂₆FN₂O₆, Hz, 1H), 7.97 (d, J = 5.2 Hz, 1H), 1529, 1482, 469.1769; found, 7.40-7.26 (m, 5H), 7.10 (td, J = 1450, 1262, 469.1784 8.3, 6.9 Hz, 1H), 6.86 (dd, J = 5.2, 1132 0.7 Hz, 1H), 6.62-6.49 (m, 3H), 5.29 (qd, J = 6.5, 5.0 Hz, 1H), 5.18 (d, J = 4.9 Hz, 1H), 4.69-4.59 (m, 1H), 3.94 (s, 3H), 1.38 (d, J = 6.4 Hz, 3H), 1.33 (d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.51, 168.70, 163.35 (d, J = 245.3 Hz), 159.04 (d, J = 10.8 Hz), 155.35, 148.73, 140.46, 136.83, 130.35, 130.12 (d, J = 10.0 Hz), 128.66, 128.41, 126.85, 111.44 (d, J = 2.9 Hz), 109.45, 108.08 (d, J = 21.4 Hz), 103.69 (d, J = 24.8 Hz), 81.45, 74.28, 56.06, 47.97, 17.99, 14.91. 128 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 11.98 ([M + H]⁺) calcd for (d, J = 0.6 Hz, 1H), 8.40 (d, J = 8.4 C₃₁H₃₀FN₂O₆, Hz, 1H), 7.94 (d, J = 5.3 Hz, 1H), 545.2082; found, 7.38-7.25 (m, 5H), 7.20-7.07 (m, 545.2090 4H), 7.07-7.00 (m, 2H), 6.85 (d, J = 5.3 Hz, 1H), 6.63-6.54 (m, 2H), 6.50 (dt, J = 10.8, 2.4 Hz, 1H), 5.20 (qd, J = 6.4, 4.3 Hz, 1H), 5.12 (d, J = 4.3 Hz, 1H), 4.94 (ddd, J = 8.5, 6.4, 5.7 Hz, 1H), 3.94 (s, 3H), 3.12 (dd, J = 14.0, 5.8 Hz, 1H), 3.06 (dd, J = 14.0, 6.4 Hz, 1H), 1.35 (d, J = 6.4 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 170.23, 168.73, 163.37 (d, J = 245.4 Hz), 158.91 (d, J = 10.9 Hz), 155.29, 148.67, 140.56, 136.79, 135.42, 130.30, 130.12 (d, J = 10.0 Hz), 129.25, 128.72, 128.59, 128.42, 127.16, 126.75, 111.52 (d, J = 2.9 Hz), 109.44, 108.05 (d, J = 21.2 Hz), 103.72 (d, J = 24.9 Hz), 81.17, 74.95, 56.06, 53.08, 37.82, 14.43. 129 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.11 ([M + Na]⁺) calcd for (s, 1H), 8.49 (d, J = 8.0 Hz, 1H), C₂₃H₂₄N₂O₆SNa, 7.98 (d, J = 5.2 Hz, 1H), 7.32-7.26 479.1253; found, (m, 1H), 7.24-7.15 (m, 2H), 7.07 479.1244. (dd, J = 3.5, 1.2 Hz, 1H), 6.96 (dd, J = 5.1, 3.5 Hz, 1H), 6.93-6.88 (m, 3H), 6.86 (d, J = 5.2 Hz, 1H), 5.50-5.35 (m, 2H), 4.79-4.65 (m, 1H), 3.94 (s, 3H), 1.47 (d, J = 7.2 Hz, 3H), 1.34-1.22 (m, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.68, 168.70, 157.64, 155.36, 148.75, 140.46, 140.15, 129.41, 126.78, 126.28, 125.92, 121.59, 115.96, 109.44, 78.29, 77.22, 73.83, 56.07, 48.02, 18.38, 16.14. 130 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.06 ([M + H]⁺) calcd for (s, 1H), 8.66 (d, J = 2.2 Hz, 1H), C₂₄H₂₆N₃O₆, 8.53 (td, J = 5.0, 1.7 Hz, 1H), 8.38 452.1821; found, (s, 1H), 7.97 (d, J = 5.3 Hz, 1H), 452.1814. 7.78 (dt, J = 7.9, 2.0 Hz, 1H), 7.31-7.27 (m, 1H), 7.23-7.14 (m, 2H), 6.92 (ddt, J = 8.5, 7.3, 1.1 Hz, 1H), 6.88-6.85 (m, 1H), 6.84-6.78 (m, 2H), 5.36-5.28 (m, 1H), 5.24 (d, J = 5.4 Hz, 1H), 4.62 (q, J = 7.4 Hz, 1H), 3.94 (s, 3H), 1.41 (d, J = 6.3 Hz, 3H), 1.32 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.41, 157.15, 149.21, 148.33, 135.34, 133.62, 129.58, 123.91, 121.85, 115.97, 109.47, 79.13, 77.22, 73.82, 56.09, 47.90, 17.90, 15.49. 131 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.10 ([M + H]⁺) calcd for (s, 1H), 8.40 (d, J = 7.8 Hz, 1H), C₂₉H₃₃N₂O₆, 7.96 (d, J = 5.1 Hz, 1H), 7.57 (dd, J = 505.2333; found, 10.0, 2.0 Hz, 3H), 7.53-7.49 (m, 505.2333. 1H), 7.46-7.40 (m, 3H), 7.39-7.30 (m, 3H), 6.87-6.82 (m, 1H), 5.20 (p, J = 6.3 Hz, 1H), 4.63-4.54 (m, 1H), 4.42 (d, J = 6.3 Hz, 1H), 3.93 (s, 3H), 3.28-3.20 (m, 2H), 1.39 (d, J = 6.3 Hz, 3H), 1.21 (d, J = 7.2 Hz, 3H), 1.08-0.98 (m, 1H), 0.54-0.44 (m, 2H), 0.18-0.07 (m, 2H). ¹³C NMR (126 MHz, CDCl₃) δ 171.42, 168.59, 155.32, 148.70, 141.20, 140.81, 140.44, 139.33, 130.43, 128.80, 128.75, 127.40, 127.09, 126.81, 126.46, 126.29, 109.40, 83.10, 74.50, 73.89, 56.05, 47.89, 17.94, 16.03, 10.61, 3.22, 2.75. 132 (Thin film) HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.19-12.04 3369, 2985, ([M + H]⁺) calcd for (m, 1H), 8.56-8.39 (m, 2939, 1742 C₂₂H₂₄N₃O₆S, 1H), 8.09-7.95 (m, 1H), 7.87-7.74 458.1379; found, (m, 1H), 7.45-7.30 (m, 1H), 458.1374 7.23 (t, J = 8.0 Hz, 2H), 6.98-6.92 (m, 3H), 6.86 (d, J = 5.2 Hz, 1H), 5.66-5.42 (m, 2H), 4.81-4.56 (m, 1H), 3.95 (s, 3H), 1.42 (d, J = 7.2 Hz, 3H), 1.38 (d, J = 6.4 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 168.69, 168.08, 157.49, 155.36, 148.74, 142.82, 142.50, 140.46, 129.60, 122.04, 120.24, 115.92, 115.57, 109.44, 79.67, 73.19, 56.08, 47.97, 18.28, 16.05. 133 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.02 ([M + H]⁺) calcd for (s, 1H), 8.39 (d, J = 8.0 Hz, 1H), C₃₁H₃₀FN₂O₆, 7.96 (d, J = 5.2 Hz, 1H), 7.60-7.50 545.2082; found, (m, 4H), 7.47-7.33 (m, 5H), 7.11 545.2098. (dd, J = 15.1, 8.2 Hz, 1H), 6.85 (d, J = 5.3 Hz, 1H), 6.64-6.55 (m, 3H), 5.34 (dt, J = 11.6, 6.6 Hz, 1H), 5.26 (d, J = 4.9 Hz, 1H), 4.69-4.60 (m, 1H), 3.94 (s, 3H), 1.42 (d, J = 6.4 Hz, 3H), 1.32 (d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.60, 168.72, 159.13, 155.34, 148.72, 141.69, 140.46, 137.50, 130.33, 130.23, 130.15, 129.16, 128.83, 127.58, 127.23, 127.13, 125.70, 125.46, 111.44, 109.44, 108.11, 103.87, 103.67, 81.54, 74.39, 56.06, 47.98, 31.87, 17.95, 14.83. 134 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.13 ([M + H]⁺) calcd for (s, 1H), 8.47 (d, J = 8.2 Hz, 1H), C₂₅H₂₅Cl₂N₂O₆, 7.95 (d, J = 5.1 Hz, 1H), 7.43-7.22 519.1089; found, (m, 6H), 6.95 (dd, J = 8.8, 2.6 Hz, 519.1077 1H), 6.86 (d, J = 5.3 Hz, 1H), 6.63 (d, J = 8.9 Hz, 1H), 5.53-5.39 (m, 1H), 5.16 (d, J = 6.8 Hz, 1H), 4.81-4.63 (m, 1H), 3.94 (s, 3H), 1.47 (d, J = 7.2 Hz, 3H), 1.24 (d, J = 6.4 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.43, 168.67, 155.34, 151.86, 148.74, 140.44, 135.93, 130.42, 130.01, 128.91, 128.82, 127.27, 127.16, 125.98, 124.14, 115.40, 109.44, 82.80, 73.57, 56.08, 48.02, 18.26, 16.18. 135 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.13 ([M + H]⁺) calcd for (d, J = 0.6 Hz, 1H), 8.48 (d, J = 8.0 C₂₅H₂₇N₂O₆, Hz, 1H), 7.97 (d, J = 5.2 Hz, 1H), 451.1869; found, 7.42-7.35 (m, 2H), 7.36-7.24 (m, 451.1868 3H), 7.22-7.08 (m, 2H), 6.93-6.79 (m, 4H), 5.53-5.33 (m, 1H), 5.13 (d, J = 6.5 Hz, 1H), 4.79-4.61 (m, 1H), 3.93 (s, 3H), 1.42 (d, J = 7.2 Hz, 3H), 1.24 (d, J = 6.5 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.71, 168.67, 157.82, 155.35, 148.75, 140.46, 137.30, 130.49, 129.35, 128.64, 128.41, 127.12, 121.09, 115.75, 109.44, 81.86, 74.06, 56.07, 48.01, 18.41, 16.35. 136 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.18 ([M + H]⁺) calcd for (s, 1H), 8.50 (d, J = 8.0 Hz, 1H), C₂₃H₃₁N₂O₆, 8.00 (d, J = 5.2 Hz, 1H), 7.39-7.27 431.2182; found, (m, 5H), 6.87 (d, J = 5.2 Hz, 1H), 431.2192 5.19 (p, J = 6.5 Hz, 1H), 4.72 (dq, J = 8.6, 7.2 Hz, 1H), 4.25 (d, J = 6.7 Hz, 1H), 3.95 (s, 3H), 3.18-2.99 (m, 2H), 1.89-1.75 (m, 1H), 1.50 (d, J = 7.2 Hz, 3H), 1.10 (d, J = 6.5 Hz, 3H), 0.89-0.81 (m, 6H). ¹³C NMR (101 MHz, CDCl₃) δ 171.63, 168.62, 155.36, 148.75, 140.45, 138.47, 130.57, 128.31, 128.10, 127.62, 109.41, 84.00, 76.10, 74.45, 56.07, 48.04, 28.63, 19.41, 19.36, 18.47, 16.34. 137 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.13 ([M + H]⁺) calcd for (s, 1H), 8.40 (d, J = 7.9 Hz, 1H), C₂₃H₃₁N₂O₆, 7.98 (d, J = 5.2 Hz, 1H), 7.43-7.21 431.2182; found, (m, 5H), 6.86 (d, J = 5.3 Hz, 1H), 431.2187 5.13 (p, J = 6.3 Hz, 1H), 4.67-4.49 (m, 1H), 4.25 (d, J = 6.1 Hz, 1H), 3.94 (s, 3H), 3.14 (dd, J = 8.8, 6.5 Hz, 1H), 3.05 (dd, J = 8.8, 6.4 Hz, 1H), 1.92-1.76 (m, 1H), 1.33 (d, J = 6.3 Hz, 3H), 1.25 (d, J = 7.2 Hz, 3H), 0.89 (d, J = 3.1 Hz, 3H), 0.87 (d, J = 3.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.40, 168.58, 155.36, 148.73, 140.44, 138.80, 130.49, 128.21, 127.94, 127.54, 109.42, 83.71, 76.27, 74.67, 56.07, 47.89, 28.63, 19.33, 18.00, 15.85. 138 (Thin film) HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.18 3372, 2964, ([M + H]⁺) calcd for (d, J = 0.6 Hz, 1H), 8.50 (d, J = 7.8 2875, 1650 C₂₂H₂₉N₂O₆, Hz, 1H), 8.00 (d, J = 5.2 Hz, 1H), 417.2025; found, 7.40-7.27 (m, 5H), 6.87 (d, J = 5.3 417.2016. Hz, 1H), 5.27-5.11 (m, 1H), 4.80-4.67 (m, 1H), 4.26 (d, J = 6.7 Hz, 1H), 3.95 (s, 3H), 3.30 (dt, J = 9.0, 6.8 Hz, 1H), 3.23 (dt, J = 9.1, 6.5 Hz, 1H), 1.60-1.53 (m, 2H), 1.50 (d, J = 7.2 Hz, 3H), 1.10 (d, J = 6.5 Hz, 3H), 0.87 (t, J = 7.4 Hz, 3H). 139 (Thin film) HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.12 3370, 2964, ([M + H]⁺) calcd for (s, 1H), 8.40 (d, J = 8.0 Hz, 1H), 2876, 1734 C₂₂H₂₉N₂O₆, 7.98 (d, J = 5.2 Hz, 1H), 7.37-7.26 417.2025; found, (m, 5H), 6.86 (d, J = 5.2 Hz, 1H), 417.2018. 5.20-5.06 (m, 1H), 4.66-4.51 (m, 1H), 4.27 (d, J = 6.1 Hz, 1H), 3.94 (s, 3H), 3.33 (dt, J = 9.1, 6.5 Hz, 1H), 3.25 (dt, J = 9.2, 6.5 Hz, 1H), 1.55 (dtd, J = 13.8, 7.4, 6.5 Hz, 2H), 1.32 (d, J = 6.3 Hz, 3H), 1.24 (d, J = 7.2 Hz, 3H), 0.89 (t, J = 7.4 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.40, 168.58, 155.35, 148.73, 140.44, 138.84, 130.50, 128.23, 127.97, 127.53, 109.41, 83.51, 74.57, 71.13, 56.08, 47.90, 23.00, 18.01, 15.87, 10.65. 140 (Thin film) HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.17 3367, 2984, ([M + H]⁺) calcd for (d, J = 0.6 Hz, 1H), 8.50 (d, J = 8.0 2938, 1739 C₂₀H₂₅N₂O₆, Hz, 1H), 8.00 (d, J = 5.2 Hz, 1H), 389.1712; found, 7.40-7.28 (m, 5H), 6.87 (d, J = 5.1 389.1713. Hz, 1H), 5.28-5.15 (m, 1H), 4.80-4.64 (m, 1H), 4.14 (d, J = 6.8 Hz, 1H), 3.95 (s, 3H), 3.24 (s, 3H), 1.51 (d, J = 7.2 Hz, 3H), 1.11 (d, J = 6.5 Hz, 3H). 141 (Thin film) HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.12 3366, 2938, ([M + H]⁺) calcd for (s, 1H), 8.40 (d, J = 8.0 Hz, 1H), 1737, 1648 C₂₀H₂₅N₂O₆, 7.98 (d, J = 5.2 Hz, 1H), 7.37-7.28 389.1712; found, (m, 5H), 6.86 (d, J = 5.2 Hz, 1H), 389.1709. 5.14 (p, J = 6.4 Hz, 1H), 4.66-4.54 (m, 1H), 4.19 (d, J = 5.9 Hz, 1H), 3.94 (s, 3H), 3.26 (s, 3H), 1.31 (d, J = 6.4 Hz, 3H), 1.26 (d, J = 7.2 Hz, 3H). 142 (Thin film) HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.18 3367, 2985, ([M + H]⁺) calcd for (d, J = 0.6 Hz, 1H), 8.51 (d, J = 8.3 2872, 1738 C₂₃H₂₉N₂O₆, Hz, 1H), 8.00 (d, J = 5.2 Hz, 1H), 429.2025; found, 7.36-7.26 (m, 5H), 6.87 (d, J = 5.3 429.2009. Hz, 1H), 5.27-5.15 (m, 1H), 4.80-4.65 (m, 1H), 4.34 (d, J = 6.8 Hz, 1H), 3.95 (s, 3H), 3.17 (dd, J = 6.8, 3.2 Hz, 2H), 1.52 (d, J = 7.2 Hz, 3H), 1.12 (d, J = 6.5 Hz, 3H), 1.03-0.93 (m, 1H), 0.53-0.34 (m, 2H), 0.16-0.05 (m, 2H). 143 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.12 ([M + H]⁺) calcd for (s, 1H), 8.40 (d, J = 7.9 Hz, 1H), C₂₉H₃₃N₂O₆, 7.97 (d, J = 5.2 Hz, 1H), 7.59-7.52 505.2330; found, (m, 4H), 7.46-7.38 (m, 4H), 7.38-7.32 505.2347. (m, 1H), 6.84 (d, J = 5.2 Hz, 1H), 5.23-5.14 (m, 1H), 4.66-4.57 (m, 1H), 4.40 (d, J = 6.2 Hz, 1H), 3.93 (s, 3H), 3.23 (d, J = 6.8 Hz, 2H), 1.38 (d, J = 6.3 Hz, 3H), 1.26 (d, J = 7.2 Hz, 3H), 1.09-0.98 (m, 1H), 0.55-0.44 (m, 2H), 0.19-0.09 (m, 2H). ¹³C NMR (126 MHz, CDCl₃) δ 171.42, 168.61, 155.35, 148.73, 140.91, 140.70, 140.45, 137.70, 130.47, 128.77, 128.02, 127.34, 127.05, 126.98, 109.40, 82.77, 74.48, 73.84, 56.06, 47.90, 18.00, 16.02, 10.60, 3.21, 2.74. 144 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.08 ([M + H]⁺) calcd for (s, 1H), 8.41 (d, J = 7.9 Hz, 1H), C₃₁H₃₁N₂O₆, 7.96 (d, J = 5.2 Hz, 1H), 7.57-7.52 527.2177; found, (m, 4H), 7.48-7.40 (m, 4H), 7.34 527.2184. (ddd, J = 7.3, 3.8, 1.2 Hz, 1H), 7.21-7.16 (m, 2H), 6.91-6.83 (m, 4H), 5.38-5.31 (m, 1H), 5.26 (d, J = 4.9 Hz, 1H), 4.67 (p, J = 7.2 Hz, 1H), 3.93 (s, 3H), 1.43 (d, J = 6.4 Hz, 3H), 1.33 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.61, 168.69, 157.86, 155.36, 148.75, 141.08, 140.52, 140.45, 136.45, 130.42, 129.40, 128.77, 127.42, 127.40, 127.26, 127.05, 121.27, 115.97, 109.43, 81.01, 74.54, 56.06, 47.96, 18.05, 15.10. 145 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.06 ([M + H]⁺) calcd for (s, 1H), 8.40 (d, J = 7.8 Hz, 1H), C₃₁H₃₁N₂O₆, 7.95 (d, J = 5.2 Hz, 1H), 7.63 (s, 527.2177; found, 1H), 7.56 (dd, J = 5.2, 3.3 Hz, 2H), 527.2187. 7.52-7.49 (m, 1H), 7.46-7.32 (m, 6H), 7.20-7.15 (m, 2H), 6.90-6.83 (m, 4H), 5.36 (dt, J = 12.2, 6.1 Hz, 1H), 5.28 (s, 1H), 4.64 (p, J = 7.2 Hz, 1H), 3.93 (s, 3H), 1.44 (d, J = 6.4 Hz, 3H), 1.28 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.65, 168.69, 157.92, 155.35, 148.73, 141.53, 140.65, 140.46, 138.18, 130.40, 129.41, 129.05, 128.81, 127.51, 127.13, 127.03, 125.85, 125.62, 121.31, 116.01, 109.43, 81.35, 74.63, 56.06, 47.95, 17.98, 15.04. 146 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.05 ([M + H]⁺) calcd for (s, 1H), 8.38 (d, J = 7.9 Hz, 1H), C₂₅H₂₆FN₂O₆, 7.96 (d, J = 5.2 Hz, 1H), 7.41-7.18 469.1775; found, (m, 5H), 6.91-6.77 (m, 3H), 6.77-6.60 469.1778 (m, 2H), 5.29 (qd, J = 6.4, 4.9 Hz, 1H), 5.11 (d, J = 4.9 Hz, 1H), 4.76-4.55 (m, 1H), 3.94 (s, 3H), 1.38 (d, J = 6.4 Hz, 3H), 1.33 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-123.13. 147 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.10 ([M + H]⁺) calcd for (s, 1H), 8.44 (d, J = 8.0 Hz, 1H), C₂₅H₂₅F₂N₂O₆, 7.97 (d, J = 5.2 Hz, 1H), 7.41-7.29 487.1680; found, (m, 2H), 7.16-6.95 (m, 2H), 6.91-6.78 487.1678 (m, 3H), 6.78-6.60 (m, 2H), 5.42-5.30 (m, 1H), 5.03 (d, J = 6.6 Hz, 1H), 4.79-4.66 (m, 1H), 3.94 (s, 3H) 1.45 (d, J = 7.2 Hz, 3H), 1.21 (d, J = 6.4 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-113.00, −122.95. 148 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.06 ([M + H]⁺) calcd for (s, 1H), 8.39 (d, J = 7.7 Hz, 1H), C₂₅H₂₆FN₂O₆, 7.97 (d, J = 5.2 Hz, 1H), 7.40-7.34 469.1769; found, (m, 2H), 7.20-7.13 (m, 2H), 7.03-6.96 469.1777. (m, 2H), 6.88 (dd, J = 15.2, 6.3 Hz, 2H), 6.82-6.78 (m, 2H), 5.31-5.24 (m, 1H), 5.18 (d, J = 5.2 Hz, 1H), 4.64 (p, J = 7.2 Hz, 1H), 3.93 (s, 3H), 1.39 (d, J = 6.4 Hz, 3H), 1.33 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-113.62. 149 HRMS-ESI (m/z) ¹H NMR (300 MHz, CDCl₃) δ 12.06 ([M + Na]⁺) calcd for (s, 1H), 8.40 (d, J = 7.6 Hz, 1H), C₂₆H₂₇ClN₂O₆Na, 7.97 (d, J = 5.3 Hz, 1H), 7.45-7.26 521.1456; found, (m, 5H), 7.12 (dd, J = 2.2, 0.8 Hz, 521.1450 1H), 6.86 (d, J = 5.2 Hz, 1H), 6.78 (ddd, J = 8.4, 2.2, 0.8 Hz, 1H), 6.54 (d, J = 8.3 Hz, 1H), 5.41-5.30 (m, 1H), 5.23 (d, J = 4.8 Hz, 1H), 4.78-4.57 (m, 1H), 3.94 (s, 3H), 2.19 (s, 3H), 1.44 (d, J = 6.4 Hz, 3H), 1.33 (d, J = 7.2 Hz, 3H). ¹³C NMR (75 MHz, CDCl₃) δ 171.60, 168.67, 155.33, 151.00, 148.71, 140.46, 136.91, 131.54, 130.72, 130.41, 128.58, 128.37, 127.85, 126.96, 123.06, 115.04, 109.41, 82.02, 74.56, 56.08, 47.97, 20.25, 18.00, 14.97. 150 HRMS-ESI (m/z) ¹H NMR (300 MHz, CDCl₃) δ 12.04 ([M + H]⁺) calcd for (s, 1H), 8.39 (d, J = 7.9 Hz, 1H), C₂₆H₂₇ClFN₂O₆, 7.98 (d, J = 5.2 Hz, 1H), 7.46-7.31 517.1541; found, (m, 2H), 7.12 (dd, J = 2.1, 0.8 Hz, 517.1537 1H), 7.08-6.92 (m, 2H), 6.86 (d, J = 5.2 Hz, 1H), 6.79 (ddd, J = 8.4, 2.2, 0.9 Hz, 1H), 6.52 (d, J = 8.4 Hz, 1H), 5.32 (qd, J = 6.4, 4.8 Hz, 1H), 5.20 (d, J = 4.9 Hz, 1H), 4.80-4.53 (m, 1H), 3.94 (s, 3H), 2.20 (s, 3H), 1.43 (d, J = 6.4 Hz, 3H), 1.35 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (471 MHz, CDCl₃) δ-113.34. 151 HRMS-ESI (m/z) ¹H NMR (300 MHz, CDCl₃) δ 12.09 ([M + H]⁺) calcd for (d, J = 0.7 Hz, 1H), 8.41 (d, J = 8.0 C₂₆H₂₉N₂O₆, Hz, 1H), 7.97 (d, J = 5.2 Hz, 1H), 465.2025; found, 7.47-7.34 (m, 2H), 7.34-7.19 (m, 465.2012 3H), 7.00-6.91 (m, 2H), 6.90-6.81 (m, 1H), 6.78-6.65 (m, 2H), 5.29 (qd, J = 6.4, 5.2 Hz, 1H), 5.15 (d, J = 5.2 Hz, 1H), 4.75-4.56 (m, 1H), 3.94 (s, 3H), 2.21 (s, 3H), 1.39 (d, J = 6.4 Hz, 3H), 1.30 (d, J = 7.2 Hz, 3H). ¹³C NMR (75 MHz, CDCl₃) δ 171.57, 168.65, 155.71, 155.35, 148.73, 140.46, 137.67, 130.46, 130.42, 129.80, 128.50, 128.14, 126.99, 115.81, 109.42, 81.36, 74.55, 56.10, 56.06, 47.93, 20.44, 18.05, 15.14. 152 HRMS-ESI (m/z) ¹H NMR (300 MHz, CDCl₃) δ 12.07 ([M + H]⁺) calcd for (d, J = 0.6 Hz, 1H), 8.39 (d, J = 7.9 C₂₆H₂₈FN₂O₆, Hz, 1H), 7.97 (d, J = 5.2 Hz, 1H), 483.1931; found, 7.47-7.31 (m, 2H), 7.05-6.93 (m, 483.1918 4H), 6.86 (dd, J = 5.3, 0.7 Hz, 1H), 6.75-6.62 (m, 2H), 5.26 (qd, J = 6.4, 5.2 Hz, 1H), 5.13 (d, J = 5.3 Hz, 1H), 4.74-4.57 (m, 1H), 3.94 (s, 3H), 2.22 (s, 3H), 1.39 (d, J = 6.4 Hz, 3H), 1.33 (d, J = 7.2 Hz, 3H). ¹³C NMR (75 MHz, CDCl₃) δ 171.51, 168.67, 162.46 (d, J = 246.8 Hz), 155.41 (d, J = 5.7 Hz), 148.75, 140.48, 133.42 (d, J = 3.3 Hz), 130.70, 130.37, 129.85, 128.73 (d, J = 8.1 Hz), 115.82, 115.64, 115.36, 109.45, 80.76, 74.34, 56.10, 47.93, 20.44, 18.05, 15.24. 153 HRMS-ESI (m/z) ¹H NMR (300 MHz, CDCl₃) δ 12.07 ([M + H]⁺) calcd for (d, J = 0.6 Hz, 1H), 8.39 (d, J = 7.9 C₂₅H₂₅F₂N₂O₆, Hz, 1H), 7.97 (d, J = 5.2 Hz, 1H), 487.1675; found, (td, J = 8.7, 6.4 Hz, 1H), 7.23-7.42 487.1690. 7.16 (m, 2H), 6.94-6.88 (m, 1H), 6.87 (d, J = 5.1 Hz, 1H), 6.85-6.74 (m, 4H), 5.49 (d, J = 5.7 Hz, 1H), 5.38 (p, J = 6.1 Hz, 1H), 4.66 (dq, J = 14.5, 7.2 Hz, 1H), 3.94 (s, 3H), 1.41 (d, J = 6.3 Hz, 3H), 1.36 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (471 MHz, CDCl₃) δ-109.47 (dt, J = 15.4, 7.9 Hz), −113.95 (dd, J = 17.3, 8.3 Hz). 154 ESIMS m/z 465 ¹H NMR (400 MHz, CDCl₃) δ 12.09 ([M + H]⁺) (s, 1H), 8.41 (d, J = 7.8 Hz, 1H), 7.97 (d, J = 5.2 Hz, 1H), 7.27 (d, J = 8.0 Hz, 2H), 7.18-7.09 (m, 4H), 6.89-6.79 (m, 4H), 5.29 (dq, J = 12.9, 6.4 Hz, 1H), 5.17 (d, J = 5.0 Hz, 1H), 4.64 (p, J = 7.3 Hz, 1H), 3.94 (s, 3H), 2.31 (s, 3H), 1.39 (d, J = 6.4 Hz, 3H), 1.33 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.57, 168.66, 157.90, 155.36, 148.74, 140.44, 137.89, 134.39, 130.45, 129.32, 129.21, 126.87, 121.10, 115.93, 109.43, 81.06, 74.59, 56.06, 47.96, 21.15, 18.06, 15.03. 155 HRMS-ESI (m/z) ¹H NMR (300 MHz, CDCl₃) δ 12.07 ([M + H]⁺) calcd for (d, J = 0.6 Hz, 1H), 8.39 (d, J = 7.8 C₂₆H₂₈FN₂O₆, Hz, 1H), 7.96 (d, J = 5.2 Hz, 1H), 483.1931; found, 7.34-7.19 (m, 2H), 7.19-7.05 (m, 483.1928 2H), 6.92-6.65 (m, 5H), 5.28 (qd, J = 6.4, 4.8 Hz, 1H), 5.08 (d, J = 4.8 Hz, 1H), 4.74-4.57 (m, 1H), 3.93 (s, 3H), 1.37 (d, J = 6.4 Hz, 3H), 1.35 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (471 MHz, CDCl₃) δ-123.34. 156 HRMS-ESI (m/z) ¹H NMR (300 MHz, CDCl₃) δ 12.04 ([M + H]⁺) calcd for (s, 1H), 8.36 (d, J = 7.8 Hz, 1H), C₂₅H₂₅F₂N₂O₆, 7.97 (d, J = 5.2 Hz, 1H), 7.41-7.28 487.1680; found, (m, 2H), 7.11-6.92 (m, 2H), 6.93-6.78 487.1678 (m, 3H), 6.78-6.62 (m, 2H), 5.26 (qd, J = 6.4, 4.9 Hz, 1H), 5.09 (d, J = 5.0 Hz, 1H), 4.72-4.57 (m, 1H), 3.94 (s, 3H), 1.37 (d, J = 6.6 Hz, 3H), 1.35 (d, J = 7.6 Hz, 3H). ¹⁹F NMR (471 MHz, CDCl₃) δ-113.40, −122.82. 157 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.09 ([M + H]⁺) calcd for (s, 1H), 8.41 (d, J = 8.0 Hz, 1H), C₂₇H₃₁N₂O₆, 7.96 (d, J = 5.2 Hz, 1H), 7.41-7.16 479.2182; found, (m, 2H), 7.10 (d, J = 7.8 Hz, 2H), 479.2180 6.94 (d, J = 8.1 Hz, 2H), 6.85 (d, J = 5.2 Hz, 1H), 6.75-6.64 (m, 2H), 5.33-5.23 (m, 1H), 5.12 (d, J = 5.0 Hz, 1H), 4.64 (p, J = 7.3 Hz, 1H), 3.93 (s, 3H), 2.30 (s, 3H), 2.20 (s, 3H), 1.38 (d, J = 6.4 Hz, 3H), 1.32 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.55, 168.66, 155.82, 155.37, 148.78, 140.41, 137.80, 134.60, 130.51, 130.35, 129.75, 129.16, 126.90, 115.84, 109.42, 81.29, 74.60, 56.04, 47.96, 21.11, 20.41, 18.07, 15.06. 158 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.11 ([M + H]⁺) calcd for (s, 1H), 8.44 (d, J = 7.7 Hz, 1H), C₂₆H₂₉N₂O₇, 7.94 (d, J = 5.2 Hz, 1H), 7.38 (d, J = 481.1969; found, 7.5 Hz, 1H), 7.26-7.21 (m, 1H), 481.1958. 7.15 (t, J = 7.8 Hz, 2H), 6.91-6.80 (m, 6H), 5.69 (d, J = 4.5 Hz, 1H), 5.45-5.38 (m, 1H), 4.66 (p, J = 7.2 Hz, 1H), 3.93 (s, 3H), 3.91 (s, 3H), 1.37-1.32 (m, 6H). ¹³C NMR (101 MHz, CDCl₃) δ 171.46, 168.67, 157.89, 156.63, 155.34, 148.75, 140.38, 130.54, 129.27, 129.14, 127.84, 125.40, 120.88, 120.86, 115.61, 110.21, 109.40, 74.91, 73.33, 56.03, 55.47, 48.01, 18.07, 14.94. 159 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.10 ([M + H]⁺) calcd for (s, 1H), 8.42 (d, J = 7.7 Hz, 1H), C₂₆H₂₈FN₂O₇, 7.95 (d, J = 5.2 Hz, 1H), 7.37-7.29 499.1875; found, (m, 1H), 7.16 (t, J = 7.9 Hz, 2H), 499.1876. 6.86 (dd, J = 11.0, 6.2 Hz, 2H), 6.79 (d, J = 8.0 Hz, 2H), 6.64-6.54 (m, 2H), 5.61 (d, J = 4.5 Hz, 1H), 5.42-5.34 (m, 1H), 4.66 (p, J = 7.2 Hz, 1H), 3.93 (s, 3H), 3.89 (s, 3H), 1.37 (d, J = 7.2 Hz, 3H), 1.34 (d, J = 6.5 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.41, 168.69, 163.41 (d, J = 246.4 Hz), 157.81 (d, J = 9.7 Hz), 157.65, 155.37, 148.76, 140.40, 130.49, 129.32, 129.02 (d, J = 10.0 Hz), 121.15 (d, J = 3.3 Hz), 121.05, 115.57, 109.43, 107.39 (d, J = 21.4 Hz), 98.69 (d, J = 25.8 Hz), 74.53, 73.20, 56.04, 55.78, 48.01, 18.06, 14.98. ¹⁹F NMR (376 MHz, CDCl₃) δ-111.20 (s, 1F). 160 ¹H NMR (300 MHz, CDCl₃) δ 12.08 (s, 1H), 8.42 (d, J = 7.9 Hz, 1H), 7.97 (d, J = 5.2 Hz, 1H), 7.37-7.23 (m, 2H), 7.20-7.06 (m, 3H), 6.85 (d, J = 5.2 Hz, 1H), 6.77 (ddd, J = 8.4, 2.2, 0.8 Hz, 1H), 6.54 (d, J = 8.4 Hz, 1H), 5.33 (qd, J = 6.4, 4.7 Hz, 1H), 5.20 (d, J = 4.7 Hz, 1H), 4.77-4.53 (m, 1H), 3.93 (s, 3H), 2.31 (s, 3H), 2.18 (s, 3H), 1.43 (d, J = 6.4 Hz, 3H), 1.36 (d, J = 7.2 Hz, 3H). 161 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.07 ([M + H]⁺) calcd for (s, 1H), 8.41 (d, J = 7.8 Hz, 1H), C₂₆H₂₉N₂O₇, 7.96 (d, J = 5.2 Hz, 1H), 7.23 (t, J = 481.1969; found, 7.9 Hz, 1H), 7.16 (dd, J = 8.4, 7.5 481.1971. Hz, 2H), 7.00-6.92 (m, 2H), 6.91-6.78 (m, 5H), 5.33-5.26 (m, 1H), 5.18 (d, J = 5.0 Hz, 1H), 4.65 (p, J = 7.3 Hz, 1H), 3.93 (s, 3H), 3.77 (s, 3H), 1.40 (d, J = 6.4 Hz, 3H), 1.33 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.58, 168.69, 159.80, 157.93, 155.36, 148.76, 140.43, 139.19, 130.45, 129.57, 129.34, 121.24, 119.31, 115.94, 113.49, 112.53, 109.44, 81.13, 74.55, 56.05, 55.21, 47.95, 18.02, 14.97. 162 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.04 ([M + H]⁺) calcd for (s, 1H), 8.37 (d, J = 7.7 Hz, 1H), C₂₆H₂₈FN₂O₆, 7.96 (d, J = 5.2 Hz, 1H), 7.37 (dd, J = 483.1926; found, 8.5, 5.9 Hz, 1H), 7.19-7.13 (m, 483.1936. 2H), 6.90-6.80 (m, 4H), 6.76-6.70 (m, 2H), 5.39 (d, J = 4.9 Hz, 1H), 5.26-5.18 (m, 1H), 4.63 (p, J = 7.2 Hz, 1H), 3.93 (s, 3H), 2.50 (s, 3H), 1.43 (d, J = 6.4 Hz, 3H), 1.29 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.66, 168.74, 162.19 (d, J = 246.5 Hz), 157.70, 155.38, 148.77, 140.44, 137.84 (d, J = 7.8 Hz), 131.39 (d, J = 3.1 Hz), 130.38, 129.42, 128.68 (d, J = 8.5 Hz), 121.32, 115.70, 117.18 (d, J = 21.2 Hz), 113.25 (d, J = 21.1 Hz), 109.48, 77.73, 73.55, 56.05, 47.95, 19.26 (d, J = 1.2 Hz), 17.86, 14.75. ¹⁹F NMR (376 MHz, CDCl₃) δ-114.75 (d, J = 2.1 Hz, 1F). 163 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.06 ([M + H]⁺) calcd for (s, 1H), 8.39 (d, J = 7.7 Hz, 1H), C₂₅H₂₅ClFN₂O₆, 7.96 (dd, J = 5.1, 0.9 Hz, 1H), 7.48 503.1380; found, (dd, J = 8.7, 6.1 Hz, 1H), 7.19 (t, J = 503.1386. 7.7 Hz, 2H), 7.09 (dd, J = 8.4, 2.4 Hz, 1H), 6.96-6.82 (m, 3H), 6.78 (d, J = 8.0 Hz, 2H), 5.63 (d, J = 5.4 Hz, 1H), 5.37 (p, J = 6.3 Hz, 1H), 4.66 (p, J = 7.3 Hz, 1H), 3.93 (d, J = 1.3 Hz, 3H), 1.42 (d, J = 6.4 Hz, 3H), 1.37 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.29, 168.71, 162.08 (d, J = 251.1 Hz), 157.07, 155.39, 148.78, 140.42, 133.93 (d, J = 10.2 Hz), 130.42, 131.14 (d, J = 3.6 Hz), 129.99 (d, J = 9.0 Hz), 129.52, 121.54, 116.71 (d, J = 24.8 Hz), 115.51, 114.83 (d, J = 21.2 Hz), 109.48, 76.63, 73.19, 56.05, 47.98, 17.95, 15.56. ¹⁹F NMR (376 MHz, CDCl₃) δ-111.13 (d, J = 3.2 Hz). 164 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.10 ([M + H]⁺) calcd for (s, 1H), 8.41 (d, J = 7.9 Hz, 1H), C₂₆H₂₈FN₂O₆, 7.97 (d, J = 5.2 Hz, 1H), 7.30 (t, J = 483.1926; found, 7.7 Hz, 1H), 7.18 (dd, J = 8.5, 7.5 483.1935. Hz, 2H), 6.85 (ddd, J = 12.2, 11.0, 7.5 Hz, 6H), 5.50 (d, J = 5.7 Hz, 1H), 5.39 (p, J = 6.2 Hz, 1H), 4.66 (p, J = 7.2 Hz, 1H), 3.94 (s, 3H), 2.29 (s, 3H), 1.41 (d, J = 6.4 Hz, 3H), 1.35 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.32, 168.64, 160.23 (d, J = 245.5 Hz), 157.37, 155.36, 148.76, 140.51 (d, J = 8.0 Hz), 140.40, 130.51, 129.42, 128.21 (d, J = 4.2 Hz), 125.34 (d, J = 2.9 Hz), 121.33, 121.31 (d, J = 13.6 Hz), 115.78, 115.58, 74.30, 73.35, 56.04, 47.93, 21.04, 18.01, 15.84. ¹⁹F NMR (376 MHz, CDCl₃) δ-119.17 (s, 1F). 165 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.05 ([M + H]⁺) calcd for (s, 1H), 8.41 (t, J = 6.4 Hz, 2H), C₂₉H₂₉N₂O₆, 7.97 (d, J = 5.2 Hz, 1H), 7.89 (d, J = 501.2020; found, 8.1 Hz, 1H), 7.80 (d, J = 8.2 Hz, 501.2031. 1H), 7.64 (t, J = 6.1 Hz, 2H), 7.53 (t, J = 7.5 Hz, 1H), 7.41 (t, J = 7.7 Hz, 1H), 7.11 (t, J = 8.0 Hz, 2H), 6.87-6.82 (m, 2H), 6.78 (d, J = 8.1 Hz, 2H), 6.11 (d, J = 4.0 Hz, 1H), 5.52-5.44 (m, 1H), 4.64 (p, J = 7.3 Hz, 1H), 3.93 (s, 3H), 1.43 (d, J = 6.5 Hz, 3H), 1.19 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.08, 168.73, 157.99, 155.37, 148.77, 140.45, 133.75, 132.92, 130.57, 130.44, 129.38, 129.03, 128.71, 126.85, 125.87, 125.47, 124.73, 122.84, 121.15, 115.63, 109.46, 77.48, 74.16, 56.05, 47.94, 17.80, 14.35. 166 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.06 ([M + H]⁺) calcd for (s, 1H), 8.39 (d, J = 7.8 Hz, 1H), C₂₉H₂₉N₂O₆, 7.95 (d, J = 5.2 Hz, 1H), 7.85 (s, 501.2020; found, 1H), 7.83-7.76 (m, 3H), 7.53 (dd, J = 501.2027. 8.5, 1.5 Hz, 1H), 7.49-7.43 (m, 2H), 7.18-7.11 (m, 2H), 6.89-6.83 (m, 4H), 5.44-5.36 (m, 2H), 4.65 (p, J = 7.3 Hz, 1H), 3.93 (s, 3H), 1.44 (d, J = 6.1 Hz, 3H), 1.28 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.60, 168.69, 157.94, 155.37, 148.76, 140.43, 135.05, 133.19, 133.10, 130.44, 129.38, 128.48, 127.92, 127.73, 126.33, 126.29, 126.22, 124.33, 121.29, 116.04, 109.45, 81.43, 74.60, 56.05, 47.96, 18.00, 14.99. 167 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.11 ([M + H]⁺) calcd for (s, 1H), 8.43 (d, J = 7.8 Hz, 1H), C₂₈H₃₀FN₂O₇, 7.96 (d, J = 5.2 Hz, 1H), 7.34 (t, J = 525.2032; found, 7.6 Hz, 1H), 7.21-7.11 (m, 2H), 525.2022. 6.84 (ddd, J = 20.4, 10.4, 7.6 Hz, 4H), 6.63-6.54 (m, 2H), 6.09 (ddt, J = 17.2, 10.4, 5.1 Hz, 1H), 5.65 (d, J = 4.5 Hz, 1H), 5.47 (ddd, J = 17.4, 3.0, 1.6 Hz, 1H), 5.44-5.38 (m, 1H), 5.35 (dd, J = 10.6, 1.3 Hz, 1H), 4.71-4.63 (m, 1H), 4.63-4.59 (m, 2H), 3.93 (s, 3H), 1.38 (d, J = 7.2 Hz, 3H), 1.34 (d, J = 6.5 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.38, 168.68, 163.23 (d, J = 246.5 Hz), 157.61, 156.70 (d, J = 9.8 Hz), 155.37, 148.77, 140.40, 132.39, 130.49, 129.32, 129.16 (d, J = 10.2 Hz), 121.38 (d, J = 3.3 Hz), 121.06, 117.99, 115.59, 109.43, 107.62 (d, J = 21.3 Hz), 99.83 (d, J = 25.8 Hz), 74.57, 73.20, 69.23, 56.04, 48.01, 18.12, 15.11. ¹⁹F NMR (376 MHz, CDCl₃) δ-111.20. 168 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.12 ([M + H]⁺) calcd for (s, 1H), 8.44 (d, J = 7.8 Hz, 1H), C₂₇H₃₀FN₂O₇, 7.95 (d, J = 5.2 Hz, 1H), 7.31 (dd, J = 513.2032; found, 8.4, 6.8 Hz, 1H), 7.19-7.13 (m, 513.1999. 2H), 6.89-6.83 (m, 2H), 6.81-6.77 (m, 2H), 6.61-6.53 (m, 2H), 5.62 (d, J = 4.3 Hz, 1H), 5.45-5.38 (m, 1H), 4.67 (p, J = 7.2 Hz, 1H), 4.09 (q, J = 7.0 Hz, 2H), 3.93 (s, 3H), 1.50 (t, J = 7.0 Hz, 3H), 1.38 (d, J = 7.2 Hz, 3H), 1.33 (d, J = 6.5 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.38, 168.69, 163.32 (d, J = 246.1 Hz), 157.70, 157.07 (d, J = 9.9 Hz), 155.36, 148.76, 140.40, 130.49, 129.30, 128.97 (d, J = 10.1 Hz), 121.10 (d, J = 3.2 Hz), 121.01, 115.57, 109.43, 107.19 (d, J = 21.4 Hz), 99.31 (d, J = 25.7 Hz), 74.70, 73.15, 64.11, 56.04, 48.03, 18.12, 14.95, 14.65. ¹⁹F NMR (376 MHz, CDCl₃) δ-111.45 (d, J = 3.1 Hz). 169 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.10 ([M + H]⁺) calcd for (s, 1H), 8.44 (d, J = 7.9 Hz, 1H), C₂₇H₂₉ClFN₂O₇, 7.95 (dd, J = 5.2, 0.7 Hz, 1H), 7.37 547.1642; found, (dd, J = 9.2, 6.6 Hz, 1H), 7.10 (d, J = 547.1642. 1.9 Hz, 1H), 6.85 (d, J = 5.2 Hz, 1H), 6.79 (dd, J = 8.4, 1.9 Hz, 1H), 6.64-6.57 (m, 2H), 6.54 (d, J = 8.4 Hz, 1H), 5.65 (d, J = 4.3 Hz, 1H), 5.45-5.38 (m, 1H), 4.68 (p, J = 7.2 Hz, 1H), 3.93 (d, J = 0.6 Hz, 3H), 3.89 (s, 3H), 2.19 (s, 3H), 1.40 (d, J = 7.2 Hz, 3H), 1.37 (d, J = 6.5 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.40, 168.68, 163.49 (d, J = 246.8 Hz), 157.80 (d, J = 9.7 Hz), 155.33, 150.82, 148.73, 140.40, 131.29, 130.67, 130.47, 129.13 (d, J = 10.1 Hz), 127.86, 122.88, 120.59 (d, J = 3.0 Hz), 114.31, 109.40, 107.47 (d, J = 21.2 Hz), 98.68 (d, J = 25.9 Hz), 75.29, 73.17, 56.03, 55.79, 48.01, 20.20, 18.06, 14.87. ¹⁹F NMR (376 MHz, CDCl₃) δ-110.85 (d, J = 2.9 Hz). 170 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.44 ([M + H]⁺) calcd for (s, 1H), 9.00 (s, 1H), 8.35 (d, J = 7.6 C₂₅H₂₆FN₂O₇, Hz, 1H), 8.09 (d, J = 5.3 Hz, 1H), 485.1719; found, 7.22 (ddd, J = 8.4, 7.0, 3.6 Hz, 3H), 485.1717. 6.97 (d, J = 5.3 Hz, 1H), 6.94 (t, J = 7.3 Hz, 1H), 6.88 (d, J = 7.8 Hz, 2H), 6.54 (td, J = 8.4, 2.5 Hz, 1H), 6.32 (dd, J = 10.0, 2.2 Hz, 1H), 5.50 (d, J = 6.9 Hz, 1H), 5.20 (p, J = 6.1 Hz, 1H), 4.65 (p, J = 7.1 Hz, 1H), 3.99 (s, 3H), 1.51 (d, J = 6.3 Hz, 3H), 1.45 (d, J = 7.1 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 170.47, 168.33, 163.09 (d, J = 246.5 Hz), 157.25, 156.26, 155.47 (d, J = 11.1 Hz), 149.58, 140.15, 130.12, 129.54, 128.71 (d, J = 10.3 Hz), 121.77, 119.93 (d, J = 3.4 Hz), 115.76, 109.65, 107.75 (d, J = 21.7 Hz), 103.82 (d, J = 24.0 Hz), 74.78, 56.25, 48.98, 29.26, 18.55, 16.20. ¹⁹F NMR (376 MHz, CDCl₃) δ-112.15. 171 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.12 ([M + H]⁺) calcd for (s, 1H), 8.43 (d, J = 7.8 Hz, 1H), C₂₈H₃₂FN₂O₇, 7.96 (d, J = 5.2 Hz, 1H), 7.32 (dd, J = 527.2188; found, 8.3, 6.8 Hz, 1H), 7.20-7.13 (m, 527.2188 2H), 6.86 (dd, J = 10.0, 6.2 Hz, 2H), 6.82-6.77 (m, 2H), 6.61-6.53 (m, 2H), 5.62 (d, J = 4.5 Hz, 1H), 5.43-5.36 (m, 1H), 4.66 (p, J = 7.2 Hz, 1H), 3.98 (t, J = 6.4 Hz, 2H), 3.94 (s, 3H), 1.96-1.86 (m, 2H), 1.37 (d, J = 7.2 Hz, 3H), 1.34 (d, J = 6.5 Hz, 3H), 1.11 (t, J = 7.4 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.38, 168.68, 163.33 (d, J = 246.1 Hz), 157.68, 157.21 (d, J = 10.0 Hz), 155.36, 148.76, 140.40, 130.49, 129.30, 128.95 (d, J = 10.2 Hz), 121.10 (d, J = 3.2 Hz), 120.99, 115.53, 109.42, 107.16 (d, J = 21.5 Hz), 99.24 (d, J = 25.9 Hz), 74.64, 73.25, 70.01, 56.04, 48.01, 22.49, 18.13, 15.03, 10.67. ¹⁹F NMR (376 MHz, CDCl₃) δ-111.41 (s, 1F). 172 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.13 ([M + H]⁺) calcd for (s, 1H), 8.46 (d, J = 7.8 Hz, 1H), C₂₇H₃₁N₂O₇, 7.94 (d, J = 5.2 Hz, 1H), 7.24 (d, J = 495.2126; found, 8.1 Hz, 1H), 7.17-7.12 (m, 2H), 495.2123. 6.83 (ddd, J = 11.1, 8.0, 6.7 Hz, 4H), 6.70 (d, J = 6.4 Hz, 2H), 5.64 (d, J = 4.4 Hz, 1H), 5.43-5.36 (m, 1H), 4.67 (p, J = 7.2 Hz, 1H), 3.93 (s, 3H), 3.89 (s, 3H), 2.31 (s, 3H), 1.36 (d, J = 7.2 Hz, 3H), 1.34 (d, J = 6.5 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.48, 168.66, 157.92, 156.54, 155.33, 148.74, 140.39, 139.23, 130.54, 129.25, 127.68, 122.28, 121.53, 120.78, 115.59, 111.11, 109.39, 74.84, 73.41, 56.03, 55.41, 48.03, 21.57, 18.11, 14.89. 173 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.11 ([M + H]⁺) calcd for (s, 1H), 8.44 (d, J = 7.8 Hz, 1H), C₂₇H₃₀FN₂O₇, 7.95 (d, J = 5.2 Hz, 1H), 7.33 (dd, J = 513.2032; found, 8.2, 6.8 Hz, 1H), 6.95 (d, J = 8.3 513.2027. Hz, 2H), 6.85 (d, J = 5.2 Hz, 1H), 6.69 (t, J = 5.7 Hz, 2H), 6.63-6.55 (m, 2H), 5.57 (d, J = 4.6 Hz, 1H), 5.40-5.33 (m, 1H), 4.66 (p, J = 7.2 Hz, 1H), 3.93 (s, 3H), 3.88 (s, 3H), 2.21 (s, 3H), 1.37 (d, J = 7.2 Hz, 3H), 1.33 (d, J = 6.5 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.43, 168.68, 163.36 (d, J = 246.2 Hz), 157.81 (d, J = 9.8 Hz), 155.53, 155.36, 148.76, 140.41, 130.49, 130.27, 129.77, 129.04 (d, J = 10.1 Hz), 121.33 (d, J = 3.2 Hz), 115.43, 109.42, 107.35 (d, J = 21.3 Hz), 98.66 (d, J = 25.9 Hz), 74.65, 73.23, 56.04, 55.77, 48.01, 20.42, 18.09, 15.00. ¹⁹F NMR (376 MHz, CDCl₃) δ-111.31 (s). 174 ESIMS m/z 533 ¹H NMR (400 MHz, CDCl₃) δ 12.08 ([M + H]⁺) (s, 1H), 8.43 (d, J = 7.9 Hz, 1H), 7.95 (d, J = 5.2 Hz, 1H), 7.36 (dd, J = 9.1, 6.7 Hz, 1H), 7.29 (dd, J = 7.9, 1.5 Hz, 1H), 7.04-6.98 (m, 1H), 6.85 (d, J = 5.2 Hz, 1H), 6.80 (td, J = 7.7, 1.1 Hz, 1H), 6.66-6.58 (m, 3H), 5.69 (d, J = 4.3 Hz, 1H), 5.43 (qd, J = 6.5, 4.4 Hz, 1H), 4.68 (p, J = 7.3 Hz, 1H), 3.94 (s, 3H), 3.90 (s, 3H), 1.40 (d, J = 7.2 Hz, 3H), 1.38 (d, J = 6.5 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.39, 168.69, 163.54 (d, J = 246.9 Hz), 157.78 (d, J = 9.7 Hz), 155.34, 153.03, 148.73, 140.40, 130.47, 130.25, 129.07 (d, J = 10.1 Hz), 127.44, 123.32, 121.58, 120.39 (d, J = 3.3 Hz), 114.39, 109.42, 107.53 (d, J = 21.3 Hz), 98.72 (d, J = 25.9 Hz), 75.25, 73.14, 56.04, 55.82, 48.01, 18.05, 14.81. ¹⁹F NMR (376 MHz, CDCl₃) δ-110.71 (s, 1F). 175 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.13 ([M + H]⁺) calcd for (s, 1H), 8.44 (d, J = 7.8 Hz, 1H), C₂₉H₃₂FN₂O₇, 7.96 (d, J = 5.2 Hz, 1H), 7.33 (dd, J = 539.2188; found, 9.2, 6.7 Hz, 1H), 7.20-7.14 (m, 539.2194. 2H), 6.85 (ddd, J = 13.7, 10.5, 7.6 Hz, 4H), 6.56 (ddd, J = 11.1, 5.1, 2.5 Hz, 2H), 5.66 (d, J = 4.5 Hz, 1H), 5.47-5.39 (m, 1H), 4.67 (p, J = 7.2 Hz, 1H), 3.94 (s, 3H), 3.89 (d, J = 6.8 Hz, 2H), 1.39 (d, J = 7.2 Hz, 3H), 1.37-1.30 (m, 4H), 0.72-0.66 (m, 2H), 0.41 (q, J = 5.1 Hz, 2H). ¹³C NMR (101 MHz, CDCl₃) δ 171.37, 168.67, 163.28 (d, J = 246.4 Hz), 157.67, 157.10 (d, J = 9.9 Hz), 155.36, 148.77, 140.40, 130.50, 129.29, 129.08 (d, J = 10.1 Hz), 121.24 (d, J = 3.4 Hz), 120.98, 115.55, 109.42, 107.25 (d, J = 21.3 Hz), 99.41 (d, J = 25.6 Hz), 74.53, 73.30, 72.96, 56.04, 48.02, 18.17, 15.18, 10.08, 3.26, 3.12. ¹⁹F NMR (376 MHz, CDCl₃) δ-111.40 (s). 176 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.09 ([M + H]⁺) calcd for (s, 1H), 8.40 (d, J = 7.8 Hz, 1H), C₂₇H₂₈F₃N₂O₇, 7.97 (d, J = 5.2 Hz, 1H), 7.37 (dd, J = 549.1843; found, 8.5, 6.6 Hz, 1H), 7.20-7.13 (m, 549.1844 2H), 6.91-6.84 (m, 2H), 6.81-6.75 (m, 2H), 6.67 (td, J = 8.3, 2.3 Hz, 1H), 6.57 (dd, J = 10.2, 2.3 Hz, 1H), 6.23 (tt, J = 54.8, 4.0 Hz, 1H), 5.60 (d, J = 4.2 Hz, 1H), 5.42-5.35 (m, 1H), 4.65 (p, J = 7.2 Hz, 1H), 4.29-4.19 (m, 2H), 3.94 (s, 3H), 1.38 (d, J = 7.2 Hz, 3H), 1.34 (d, J = 6.5 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.42, 168.69, 163.14 (d, J = 247.8 Hz), 157.52, 155.56 (d, J = 9.8 Hz), 155.39, 148.77, 140.42, 130.43, 129.51 (d, J = 9.9 Hz), 129.40, 121.72 (d, J = 3.4 Hz), 121.26, 115.55, 113.24 (t, J = 241.4 Hz), 109.46, 108.86 (d, J = 21.2 Hz), 99.64 (d, J = 26.1 Hz), 74.59, 73.00, 67.61 (t, J = 29.7 Hz), 56.05, 48.01, 18.05, 14.73. ¹⁹F NMR (376 MHz, CDCl₃) δ-110.47 (s), −124.95 (d, J = 296.7 Hz), −125.91 (d, J = 296.7 Hz). 177 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.14 ([M + H]⁺) calcd for (s, 1H), 8.46 (d, J = 7.9 Hz, 1H), C₂₈H₃₃N₂O₇, 7.95 (d, J = 5.2 Hz, 1H), 7.24 (d, J = 509.2282; found, 7.5 Hz, 1H), 6.94 (d, J = 8.2 Hz, 509.2284. 2H), 6.85 (d, J = 5.2 Hz, 1H), 6.73-6.67 (m, 4H), 5.59 (d, J = 4.4 Hz, 1H), 5.42-5.35 (m, 1H), 4.66 (p, J = 7.2 Hz, 1H), 3.93 (s, 3H), 3.88 (s, 3H), 2.31 (s, 3H), 2.20 (s, 3H), 1.36 (d, J = 7.2 Hz, 3H), 1.33 (d, J = 6.5 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.49, 168.65, 156.56, 155.81, 155.34, 148.74, 140.38, 139.13, 130.57, 129.94, 129.70, 127.70, 122.47, 121.52, 115.44, 111.09, 109.37, 74.98, 73.45, 56.03, 55.39, 48.02, 21.56, 20.41, 18.13, 14.89. 178 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.10 ([M + H]⁺) calcd for (s, 1H), 8.43 (d, J = 7.8 Hz, 1H), C₂₇H₃₀FN₂O₇, 7.95 (d, J = 5.2 Hz, 1H), 7.47 (dd, J = 561.2032; found, 8.7, 6.5 Hz, 1H), 7.45-7.39 (m, 561.2030. 2H), 7.24-7.15 (m, 3H), 7.11-7.06 (m, 2H), 6.87 (ddd, J = 11.6, 9.4, 6.2 Hz, 4H), 6.71 (td, J = 8.3, 2.5 Hz, 1H), 6.48 (dd, J = 10.1, 2.5 Hz, 1H), 5.72 (d, J = 4.9 Hz, 1H), 5.54-5.47 (m, 1H), 4.70 (p, J = 7.2 Hz, 1H), 3.93 (s, 3H), 1.44-1.38 (m, 6H). ¹⁹F NMR (376 MHz, CDCl₃) δ-110.54-−110.75 (m). 179 ESIMS m/z 595 ¹H NMR (300 MHz, CDCl₃) δ 12.08 ([M + H]⁺) (s, 1H), 8.43 (d, J = 7.9 Hz, 1H), 7.96 (d, J = 5.2 Hz, 1H), 7.53 (dd, J = 8.7, 6.5 Hz, 1H), 7.45-7.38 (m, 2H), 7.31 (dd, J = 7.9, 1.6 Hz, 1H), 7.22 (dt, J = 8.4, 1.0 Hz, 1H), 7.09-7.00 (m, 3H), 6.87-6.81 (m, 2H), 6.79-6.71 (m, 2H), 6.49 (dd, J = 10.1, 2.5 Hz, 1H), 5.80 (d, J = 4.5 Hz, 1H), 5.59-5.52 (m, 1H), 4.71 (p, J = 7.2 Hz, 1H), 3.93 (s, 3H), 1.45 (d, J = 6.5 Hz, 3H), 1.43 (d, J = 7.3 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-110.16 (s). 180 ¹H NMR (300 MHz, CDCl₃) δ 12.24 (s, 1H), 8.51 (d, J = 7.9 Hz, 1H), 7.98 (d, J = 5.2 Hz, 1H), 7.39-7.27 (m, 5H), 6.87 (d, J = 5.2 Hz, 1H), 5.07 (dd, J = 6.8, 4.8 Hz, 1H), 4.85-4.69 (m, 1H), 4.26 (d, J = 6.8 Hz, 1H), 3.95 (s, 3H), 3.19 (s, 3H), 1.83-1.66 (m, 1H), 1.56 (d, J = 7.1 Hz, 3H), 0.90 (d, J = 6.9 Hz, 3H), 0.89 (d, J = 6.8 Hz, 3H). ¹³C NMR (75 MHz, CDCl₃) δ 171.86, 168.59, 155.30, 148.70, 140.42, 137.92, 130.58, 128.59, 128.30, 127.51, 109.37, 83.45, 81.46, 57.02, 48.05, 28.26, 19.78, 18.62, 16.72 181 ESIMS m/z 543 ¹H NMR (400 MHz, CDCl₃) δ 12.12 ([M + H]⁺) (s, 1H), 8.46 (d, J = 7.9 Hz, 1H), 7.95 (d, J = 5.2 Hz, 1H), 7.26 (d, J = 7.7 Hz, 1H), 7.10 (d, J = 1.9 Hz, 1H), 6.84 (d, J = 5.2 Hz, 1H), 6.78 (dd, J = 8.4, 1.6 Hz, 1H), 6.73-6.68 (m, 2H), 6.55 (d, J = 8.4 Hz, 1H), 5.67 (d, J = 4.2 Hz, 1H), 5.43 (qd, J = 6.4, 4.3 Hz, 1H), 4.68 (p, J = 7.2 Hz, 1H), 3.93 (s, 3H), 3.88 (s, 3H), 2.31 (s, 3H), 2.18 (s, 3H), 1.39 (d, J = 7.2 Hz, 3H), 1.37 (d, J = 6.5 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.46, 168.66, 156.53, 155.31, 151.08, 148.72, 140.38, 139.44, 130.90, 130.55, 127.84, 127.71, 122.75, 121.72, 121.61, 114.28, 111.08, 109.36, 75.59, 73.42, 56.02, 55.41, 48.03, 21.58, 20.20, 18.10, 14.78. 182 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.31-8.22 [M]⁺ calcd for (m, 2H), 7.36-7.20 (m, 5H), C₂₆H₃₂N₂O₈, 6.94 (d, J = 5.4 Hz, 1H), 5.78-5.68 500.2159; found, (m, 2H), 5.12 (h, J = 6.4 Hz, 1H), 500.2165 4.68-4.55 (m, 1H), 4.33 (d, J = 6.4 Hz, 1H), 3.90 (s, 3H), 3.19 (dd, J = 6.8, 2.4 Hz, 2H), 2.06 (s, 3H), 1.35 (d, J = 6.3 Hz, 3H), 1.17 (d, J = 7.1 Hz, 3H), 1.01 (ttt, J = 8.0, 6.7, 4.9 Hz, 1H), 0.54-0.41 (m, 2H), 0.19-0.04 (m, 2H). ¹³C NMR (126 MHz, CDCl₃) δ 172.03, 170.27, 162.86, 160.26, 145.68, 143.97, 142.51, 138.81, 128.21, 127.95, 127.60, 109.52, 89.56, 83.08, 74.22, 73.75, 56.17, 48.08, 20.87, 18.13, 16.07, 10.59, 3.17, 2.71. 183 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.32-8.26 [M]⁺ calcd for (m, 1H), 8.24 (d, J = 5.4 Hz, C₂₈H₃₀N₂O₈, 1H), 7.44-7.21 (m, 5H), 7.22-7.08 522.2002; found, (m, 2H), 6.94-6.89 (m, 1H), 522.2005 6.89-6.78 (m, 3H), 5.77-5.67 (m, 2H), 5.33-5.25 (m, 1H), 5.21 (d, J = 5.1 Hz, 1H), 4.66 (p, J = 7.2 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.39 (d, J = 6.4 Hz, 3H), 1.26 (d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.22, 170.27, 162.94, 160.26, 157.88, 145.68, 144.00, 142.41, 137.59, 129.33, 128.50, 128.14, 126.98, 121.15, 115.97, 109.55, 89.55, 81.23, 74.29, 56.17, 48.12, 20.87, 18.18, 15.10. 184 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.50-8.42 [M]⁺ calcd for (m, 1H), 8.33-8.23 (m, 1H), C₂₇H₂₈N₂O₇, 7.42-7.35 (m, 2H), 7.34-7.20 (m, 492.1897; found, 3H), 7.20-7.11 (m, 2H), 7.01-6.92 492.1900 (m, 1H), 6.90-6.76 (m, 3H), 5.32-5.16 (m, 2H), 4.64 (tt, J = 10.1, 5.1 Hz, 1H), 3.86 (s, 3H), 2.38 (s, 3H), 1.38 (d, J = 6.3 Hz, 3H), 1.24 (d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.08, 168.87, 162.36, 159.40, 157.85, 146.63, 141.41, 137.54, 137.45, 129.32, 128.49, 128.13, 126.97, 121.15, 115.96, 109.76, 81.19, 74.29, 56.24, 47.89, 20.74, 18.32, 15.09. 185 (Thin film) HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.31-8.26 3376.11, 2985.22, ([M + H]⁺) calcd for (m, 2H), 7.43-7.36 (m, 2H), 1739.53, 1675.70, C₂₈H₃₁N₂O₈, 7.34-7.28 (m, 2H), 7.26-7.21 (m, 1493.93, 1200.10 523.2075; found, 1H), 7.20-7.13 (m, 2H), 6.95 (d, J = 523.2075 5.4 Hz, 1H), 6.91-6.80 (m, 3H), 5.75-5.71 (m, 2H), 5.32-5.18 (m, 2H), 4.74-4.60 (m, 1H), 3.91 (s, 3H), 2.05 (s, 3H), 1.43 (d, J = 7.1 Hz, 3H), 1.36 (d, J = 6.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.07, 170.27, 162.88, 160.30, 157.87, 145.67, 144.08, 142.45, 137.56, 129.33, 128.50, 128.06, 126.83, 121.16, 116.07, 109.55, 89.61, 81.11, 74.54, 56.19, 48.16, 20.87, 18.37, 14.52. 186 (Thin film) HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.28 3378.15, 2984.35, ([M + H]⁺) calcd for (d, J = 7.8 Hz, 1H), 8.24 (d, J = 5.4 1740.49, 1674.69, C₂₈H₃₁N₂O₈, Hz, 1H), 7.43-7.37 (m, 2H), 7.36-7.21 1493.07, 1199.65 523.2075; found, (m, 3H), 7.20-7.13 (m, 2H), 523.2087 6.93 (d, J = 5.4 Hz, 1H), 6.90-6.79 (m, 3H), 5.74 (d, J = 6.4 Hz, 1H), 5.71 (d, J = 6.4 Hz, 1H), 5.33-5.18 (m, 2H), 4.67 (dq, J = 11.0, 7.2 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.39 (d, J = 6.4 Hz, 3H), 1.26 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.22, 170.27, 162.95, 160.27, 157.90, 145.68, 144.01, 142.44, 137.61, 129.34, 128.51, 128.14, 126.99, 121.16, 115.99, 109.55, 89.57, 81.26, 74.31, 56.18, 48.14, 20.88, 18.20, 15.11. 187 (Thin film) HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.30-8.22 3380, 2970, ([M + H]⁺) calcd for (m, 2H), 7.41-7.24 (m, 5H), 1740, 1675, C₂₈H₃₀FN₂O₈, 7.10 (td, J = 8.3, 6.7 Hz, 1H), 6.93 1504, 1488, 541.1981; found, (d, J = 5.4 Hz, 1H), 6.64-6.50 (m, 1202, 1132 541.1990 3H), 5.76-5.68 (m, 2H), 5.32-5.21 (m, 1H), 5.19 (d, J = 4.9 Hz, 1H), 4.67 (p, J = 7.2 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.38 (d, J = 6.4 Hz, 3H), 1.28 (d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.19, 170.29, 163.36 (d, J = 245.4 Hz), 162.98, 160.27, 159.11 (d, J = 10.9 Hz), 145.68, 144.03, 142.37, 136.95, 130.10 (d, J = 10.0 Hz), 128.63, 128.35, 126.88, 111.55 (d, J = 3.0 Hz), 109.57, 108.03 (d, J = 21.3 Hz), 103.73 (d, J = 24.8 Hz), 89.56, 81.50, 74.07, 56.17, 48.15, 20.88, 18.16, 14.93. ¹⁹F NMR (471 MHz, CDCl₃) δ-111.61 (dt, J = 10.9, 7.7 Hz). 188 (Thin film) HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.45 3380, 2970, ([M + H]⁺) calcd for (br s, 1H), 8.29 (d, J = 5.4 Hz, 1H), 2941, 1768, C₂₇H₂₈FN₂O₇, 7.40-7.26 (m, 5H), 7.10 (td, J = 1738, 1676, 511.1875; found, 8.3, 6.8 Hz, 1H), 6.99 (d, J = 5.5 Hz, 1507, 1488, 511.1883 1H), 6.63-6.50 (m, 3H), 5.26 (qd, J = 1199, 1132 6.4, 4.7 Hz, 1H), 5.18 (d, J = 4.9 Hz, 1H), 4.65 (p, J = 7.4 Hz, 1H), 3.90 (s, 3H), 2.39 (s, 3H), 1.36 (d, J = 6.4 Hz, 3H), 1.27 (d, J = 7.1 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.08, 168.91, 163.36 (d, J = 245.5 Hz), 162.41, 159.43, 159.10 (d, J = 11.0 Hz), 146.63, 141.41, 137.49, 136.92, 130.08 (d, J = 10.0 Hz), 128.62, 128.35, 126.89, 111.56 (d, J = 2.9 Hz), 109.76, 108.02 (d, J = 21.2 Hz), 103.73 (d, J = 24.9 Hz), 81.47, 74.09, 56.27, 47.93, 20.75, 18.31, 14.91. ¹⁹F NMR (471 MHz, CDCl₃) δ-111.63 (dt, J = 10.9, 7.7 Hz). 189 (Thin film) HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.29 3379, 2970, ([M + H]⁺) calcd for (d, J = 8.3 Hz, 1H), 8.22 (d, J = 5.4 1740, 1676, C₃₄H₃₄FN₂O₈, Hz, 1H), 7.39-7.25 (m, 5H), 7.18-7.06 1488, 1200 617.2294; found, (m, 4H), 7.05-6.99 (m, 2H), 617.2304 6.92 (d, J = 5.4 Hz, 1H), 6.64-6.56 (m, 2H), 6.52 (dt, J = 10.8, 2.4 Hz, 1H), 5.71-5.64 (m, 2H), 5.21-5.10 (m, 2H), 4.99 (dt, J = 8.5, 5.9 Hz, 1H), 3.90 (s, 3H), 3.07 (qd, J = 13.9, 6.0 Hz, 2H), 2.04 (d, J = 2.0 Hz, 3H), 1.34 (d, J = 6.4 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 170.84, 170.27, 163.38 (d, J = 245.5 Hz), 163.01, 160.23, 158.97 (d, J = 10.9 Hz), 145.72, 144.01, 142.22, 136.91, 135.85, 130.10 (d, J = 10.0 Hz), 129.37, 128.70, 128.42, 128.37, 126.92, 126.77, 111.62 (d, J = 2.9 Hz), 109.56, 107.99 (d, J = 21.3 Hz), 103.75 (d, J = 24.9 Hz), 89.54, 81.19, 74.80, 56.16, 53.30, 37.83, 20.87, 14.34. ¹⁹F NMR (471 MHz, CDCl₃) δ-111.61 (dt, J = 10.8, 7.6 Hz). 190 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.45 ([M + H]⁺) calcd for (d, J = 8.4 Hz, 1H), 8.25 (d, J = 5.5 C₃₃H₃₂FN₂O₇, Hz, 1H), 7.39-7.24 (m, 5H), 7.17-7.03 587.2188; found, (m, 4H), 7.02-6.94 (m, 3H), 587.2184 6.65-6.55 (m, 2H), 6.52 (dt, J = 10.9, 2.4 Hz, 1H), 5.19-5.08 (m, 2H), 4.97 (dt, J = 8.5, 5.6 Hz, 1H), 3.89 (s, 3H), 3.09 (app d, J = 5.7 Hz, 2H), 2.39 (s, 3H), 1.32 (d, J = 6.3 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 170.67, 168.88, 163.40 (d, J = 245.3 Hz), 162.47, 159.39, 158.97 (d, J = 10.9 Hz), 146.72, 141.37, 137.49, 136.88, 135.69, 130.10 (d, J = 9.9 Hz), 129.43, 128.71, 128.42, 128.37, 126.95, 126.77, 111.64 (d, J = 2.9 Hz), 109.79, 107.98 (d, J = 21.3 Hz), 103.76 (d, J = 24.8 Hz), 81.14, 74.87, 56.27, 53.09, 37.85, 20.77, 14.26. ¹⁹F NMR (376 MHz, CDCl₃) δ-111.61. 191 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.31-8.22 ([M + H]⁺) calcd for (m, 2H), 7.44-7.27 (m, 5H), C₂₈H₂₉F₂N₂O₈, 7.02-6.91 (m, 2H), 6.58-6.44 (m, 559.1886; found, 2H), 5.77-5.68 (m, 2H), 5.33 (qd, J = 559.1909 6.4, 5.0 Hz, 1H), 5.20 (d, J = 5.1 Hz, 1H), 4.73-4.60 (m, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.41 (d, J = 6.4 Hz, 3H), 1.28 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.15, 170.28, 162.99, 160.27, 158.32 (dd, J = 242.3, 2.7 Hz), 149.47 (dd, J = 242.0, 3.2 Hz), 146.24 (dd, J = 12.5, 10.5 Hz), 145.69, 144.00, 142.41, 136.31, 128.68, 128.65, 127.01, 116.38 (dd, J = 21.0, 10.2 Hz), 109.58, 107.65 (dd, J = 23.8, 6.9 Hz), 105.13 (dd, J = 27.2, 1.4 Hz), 89.53, 83.05, 73.87, 56.18, 48.14, 20.86, 18.06, 15.10. ¹⁹F NMR (376 MHz, CDCl₃) δ-116.68 (d, J = 15.0 Hz), −138.67 (d, J = 15.0 Hz). 192 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.46 ([M + H]⁺) calcd for (d, J = 8.0 Hz, 1H), 8.29 (d, J = 5.4 C₂₇H₂₇F₂N₂O₇, Hz, 1H), 7.43-7.25 (m, 5H), 7.04-6.91 529.1781; found, (m, 2H), 6.57-6.43 (m, 2H), 529.1784 5.31 (qd, J = 6.5, 5.1 Hz, 1H), 5.18 (d, J = 5.1 Hz, 1H), 4.65 (dq, J = 8.3, 7.2 Hz, 1H), 3.89 (s, 3H), 2.39 (s, 3H), 1.40 (d, J = 6.4 Hz, 3H), 1.27 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.04, 168.90, 162.43, 159.44, 158.32 (dd, J = 242.3, 2.5 Hz), 149.46 (dd, J = 242.1, 3.2 Hz), 146.63, 146.23 (dd, J = 12.3, 10.8 Hz), 141.42, 137.50, 136.28, 128.67, 128.65, 127.00, 116.35 (dd, J = 20.9, 10.1 Hz), 109.77, 107.62 (dd, J = 23.8, 7.0 Hz), 105.11 (dd, J = 27.3, 1.3 Hz), 82.99, 73.90, 56.27, 47.94, 20.75, 18.19, 15.03. ¹⁹F NMR (376 MHz, CDCl₃) δ-116.69 (d, J = 15.0 Hz), −138.71 (d, J = 14.9 Hz). 193 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.35-8.22 ([M + H]⁺) calcd for (m, 2H), 7.44-7.27 (m, 5H), C₂₉H₃₁F₂N₂O₈, 7.02-6.91 (m, 2H), 6.58-6.42 (m, 573.2043; found, 2H), 5.78-5.68 (m, 2H), 5.32 (qd, J = 573.2058 6.4, 5.0 Hz, 1H), 5.19 (d, J = 5.0 Hz, 1H), 4.66 (ddd, J = 8.3, 6.6, 5.2 Hz, 1H), 3.91 (s, 3H), 2.06 (s, 3H), 1.87-1.75 (m, 1H), 1.69-1.57 (m, 1H), 1.41 (d, J = 6.4 Hz, 3H), 0.75 (t, J = 7.4 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.51, 170.28, 163.14, 160.30, 158.33 (dd, J = 239.9, 2.6 Hz), 149.43 (dd, J = 241.9, 3.2 Hz), 146.24 (dd, J = 12.4, 10.6 Hz), 145.69, 144.04, 142.42, 136.32, 128.71, 128.66, 126.98, 116.35 (dd, J = 21.0, 10.0 Hz), 109.55, 107.58 (dd, J = 23.9, 7.0 Hz), 105.00 (dd, J = 27.3, 1.4 Hz), 89.60, 82.99, 73.97, 56.18, 53.27, 25.41, 20.87, 15.09, 9.21. ¹⁹F NMR (376 MHz, CDCl₃) δ-116.70 (d, J = 15.0 Hz), −138.70 (d, J = 14.9 Hz). 194 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.49 ([M + H]⁺) calcd for (d, J = 8.6 Hz, 1H), 8.30 (d, J = 5.4 C₂₈H₂₉F₂N₂O₇, Hz, 1H), 7.43-7.27 (m, 5H), 7.02-6.91 543.1937; found, (m, 2H), 6.57-6.42 (m, 2H), 543.1948 5.30 (qd, J = 6.4, 4.9 Hz, 1H), 5.19 (d, J = 5.0 Hz, 1H), 4.64 (ddd, J = 8.5, 6.5, 5.2 Hz, 1H), 3.89 (s, 3H), 2.39 (s, 3H), 1.86-1.72 (m, 1H), 1.68-1.56 (m, 1H), 1.40 (d, J = 6.4 Hz, 3H), 0.74 (t, J = 7.4 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.38, 168.89, 162.60, 159.44, 158.31 (dd, J = 242.3, 2.6 Hz), 149.42 (dd, J = 242.0, 3.4 Hz), 146.65, 146.23 (dd, J = 12.4, 10.6 Hz), 141.47, 137.49, 136.29, 128.70, 128.65, 126.96, 116.32 (dd, J = 20.9, 10.2 Hz), 109.75, 107.54 (dd, J = 23.8, 6.8 Hz), 104.98 (dd, J = 27.2, 1.7 Hz), 82.92, 73.99, 56.27, 53.07, 25.48, 20.75, 15.02, 9.13. ¹⁹F NMR (376 MHz, CDCl₃) δ-116.69 (d, J = 15.0 Hz), −138.73 (d, J = 15.0 Hz). 195 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.26 ([M + H]⁺) calcd for (d, J = 7.8 Hz, 1H), 8.22 (d, J = 5.4 C₂₉H₃₀F₃N₂O₈, Hz, 1H), 7.45-7.26 (m, 7H), 6.96-6.84 591.1949; found, (m, 3H), 5.76-5.67 (m, 2H), 591.1953 5.34-5.24 (m, 2H), 4.67 (p, J = 7.3 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.39 (d, J = 6.1 Hz, 3H), 1.30 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.15, 170.28, 163.04, 160.28, 160.18, 145.66, 144.02, 142.32, 136.59, 128.72, 128.47, 126.82, 126.75 (q, J = 3.9 Hz), 124.33 (q, J = 259.5 Hz), 123.21 (q, J = 32.7 Hz), 115.78, 109.58, 89.54, 81.31, 73.99, 56.16, 48.23, 20.86, 18.09, 14.76. ¹⁹F NMR (376 MHz, CDCl₃) δ-61.61. 196 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.44 ([M + H]⁺) calcd for (d, J = 8.2 Hz, 1H), 8.25 (d, J = 5.4 C₂₈H₂₈F₃N₂O₇, Hz, 1H), 7.43-7.28 (m, 7H), 6.97 561.1843; found, (d, J = 5.5 Hz, 1H), 6.90-6.86 (m, 561.1853 2H), 5.33-5.22 (m, 2H), 4.72-4.59 (m, 1H), 3.89 (s, 3H), 2.39 (s, 3H), 1.37 (d, J = 6.0 Hz, 3H), 1.29 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.03, 168.88, 162.48, 160.16, 159.43, 146.59, 141.35, 137.51, 136.57, 128.71, 128.46, 126.82, 126.77 (q, J = 4.2 Hz), 124.29 (q, J = 271.2 Hz), 123.19 (q, J = 32.6 Hz), 115.79, 109.77, 81.27, 74.04, 56.26, 48.02, 20.75, 18.24, 14.71. ¹⁹F NMR (376 MHz, CDCl₃) δ-61.60. 197 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.34 ([M + H]⁺) calcd for (d, J = 9.2 Hz, 1H), 8.21 (d, J = 5.3 C₃₁H₃₄F₃N₂O₈, Hz, 1H), 7.44-7.27 (m, 7H), 6.93 619.2262; found, (d, J = 5.4 Hz, 1H), 6.90-6.83 (m, 619.2266 2H), 5.77-5.67 (m, 2H), 5.29 (q, J = 2.4, 1.9 Hz, 2H), 4.64 (dd, J = 9.1, 4.8 Hz, 1H), 3.90 (s, 3H), 2.20-2.08 (m, 1H), 2.06 (s, 3H), 1.40-1.34 (m, 3H), 0.90 (d, J = 6.8 Hz, 3H), 0.77 (d, J = 6.8 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.20, 170.26, 163.35, 160.36, 160.16, 145.63, 144.13, 142.28, 136.52, 128.74, 128.45, 126.77, 126.72 (q, J = 3.9 Hz), 124.28 (q, J = 271.3 Hz), 123.16 (q, J = 32.9 Hz), 115.72, 109.55, 89.64, 81.19, 74.05, 57.21, 56.16, 31.25, 20.86, 19.10, 17.46, 14.55. ¹⁹F NMR (376 MHz, CDCl₃) δ-61.61. 198 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.48 ([M + H]⁺) calcd for (d, J = 9.4 Hz, 1H), 8.24 (d, J = 5.4 C₃₀H₃₂F₃N₂O₇, Hz, 1H), 7.43-7.29 (m, 7H), 6.97 589.2156; found, (d, J = 5.5 Hz, 1H), 6.89-6.82 (m, 589.2158 2H), 5.31-5.23 (m, 2H), 4.60 (dd, J = 9.4, 4.8 Hz, 1H), 3.89 (s, 3H), 2.39 (s, 3H), 2.17-2.04 (m, 1H), 1.35 (d, J = 6.1 Hz, 3H), 0.89 (d, J = 6.8 Hz, 3H), 0.77 (d, J = 6.8 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.04, 168.87, 162.80, 160.15, 159.43, 146.60, 141.48, 137.50, 136.50, 128.73, 128.44, 126.76, 126.70 (q, J = 3.7 Hz), 124.30 (q, J = 269.7 Hz), 123.13 (q, J = 33.0 Hz), 115.73, 109.72, 81.14, 74.08, 57.04, 56.25, 31.31, 20.76, 19.00, 17.48, 14.46. ¹⁹F NMR (376 MHz, CDCl₃) δ-61.60. 199 (Thin film) HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.28-8.21 3382, 2987, ([M + H]⁺) calcd for (m, 2H), 7.40-7.27 (m, 6H), 2941, 1742, C₂₈H₂₉Cl₂N₂O₈, 6.97-6.91 (m, 2H), 6.57 (d, J = 8.9 1674, 1574, 591.1295; found, Hz, 1H), 5.75-5.67 (m, 2H), 5.32 1504, 1478, 591.1301 (qd, J = 6.4, 4.6 Hz, 1H), 5.24 (d, J = 1200, 729 4.6 Hz, 1H), 4.67 (p, J = 7.3 Hz, 1H), 3.91 (s, 3H), 2.07 (s, 3H), 1.42 (d, J = 6.4 Hz, 3H), 1.32 (d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.17, 170.29, 163.04, 160.25, 152.05, 145.67, 144.00, 142.33, 136.30, 129.96, 128.71, 128.56, 127.34, 126.83, 126.04, 124.28, 115.75, 109.54, 89.55, 82.31, 74.15, 56.18, 48.24, 20.88, 18.08, 14.69. 200 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.43 ([M + H]⁺) calcd for (s, 1H), 8.28 (d, J = 5.5 Hz, 1H), C₂₇H₂₇Cl₂N₂O₇, 7.40-7.27 (m, 6H), 6.98 (d, J = 5.5 561.1190; found, Hz, 1H), 6.92 (dd, J = 8.9, 2.5 Hz, 561.1207 1H), 6.56 (d, J = 8.9 Hz, 1H), 5.33-5.25 (m, 1H), 5.23 (d, J = 4.5 Hz, 1H), 4.65 (p, J = 7.4 Hz, 1H), 3.91 (s, 3H), 2.38 (s, 3H), 1.40 (d, J = 6.5 Hz, 3H), 1.31 (d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.06, 168.90, 162.48, 159.40, 152.04, 146.60, 141.34, 137.47, 136.28, 129.92, 128.70, 128.55, 127.33, 126.80, 126.01, 124.26, 115.76, 109.73, 82.25, 74.19, 56.28, 48.03, 20.75, 18.20, 14.59. 201 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.28-8.21 ([M + H]⁺) calcd for (m, 2H), 7.39-7.25 (m, 5H), C₂₈H₃₀ClN₂O₈, 7.12-7.07 (m, 2H), 6.93 (d, J = 5.4 557.1685; found, Hz, 1H), 6.77-6.71 (m, 2H), 5.72 557.1702 (app q, J = 6.5 Hz, 2H), 5.27 (qd, J = 6.5, 4.8 Hz, 1H), 5.16 (d, J = 4.9 Hz, 1H), 4.66 (p, J = 7.3 Hz, 1H), 3.91 (s, 3H), 2.06 (s, 3H), 1.37 (d, J = 6.4 Hz, 3H), 1.29 (d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.17, 170.29, 163.00, 160.27, 156.41, 145.66, 144.03, 142.33, 137.00, 129.23, 128.62, 128.33, 126.88, 126.02, 117.21, 109.56, 89.56, 81.58, 74.11, 56.18, 48.20, 20.88, 18.13, 14.81. 202 (Thin film) HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.30-8.22 3379, 2986, ([M + H]⁺) calcd for (m, 2H), 7.41-7.26 (m, 5H), 2940, 1742, C₂₈H₃₀ClN₂O₈, 7.11-7.03 (m, 1H), 6.93 (d, J = 5.4 1675, 1593, 557.1685; found, Hz, 1H), 6.89-6.83 (m, 2H), 6.72-6.66 1578, 1504, 557.1688 (m, 1H), 5.76-5.68 (m, 2H), 1201, 1002 5.32-5.22 (m, 1H), 5.19 (d, J = 4.9 Hz, 1H), 4.66 (p, J = 7.4 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.37 (d, J = 6.4 Hz, 3H), 1.28 (d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.18, 170.28, 162.98, 160.26, 158.52, 145.68, 144.02, 142.35, 136.86, 134.68, 130.13, 128.64, 128.37, 126.88, 121.41, 116.58, 114.03, 109.57, 89.56, 81.44, 74.08, 56.17, 48.16, 20.88, 18.16, 14.89. 203 (Thin film) HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.45 3380, 2985, ([M + H]⁺) calcd for (br s, 1H), 8.29 (d, J = 5.4 Hz, 1H), 2940, 1769, C₂₇H₂₈ClN₂O₇, 7.40-7.26 (m, 5H), 7.10-7.03 (m, 1737, 1676, 527.1580; found, 1H), 6.98 (d, J = 5.5 Hz, 1H), 6.88-6.82 1592, 1507, 527.1590 (m, 2H), 6.72-6.66 (m, 1H), 1197, 1174 5.30-5.22 (m, 1H), 5.18 (d, J = 4.9 Hz, 1H), 4.65 (p, J = 7.4 Hz, 1H), 3.90 (s, 3H), 2.39 (s, 3H), 1.36 (d, J = 6.4 Hz, 3H), 1.27 (d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.06, 168.90, 162.41, 159.42, 158.51, 146.63, 141.40, 137.48, 136.83, 134.68, 130.11, 128.64, 128.37, 126.88, 121.39, 116.58, 114.04, 109.76, 81.41, 74.10, 56.27, 47.93, 20.76, 18.31, 14.87. 204 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.30-8.22 ([M + H]⁺) calcd for (m, 2H), 7.44-7.38 (m, 2H), C₂₈H₃₀ClN₂O₈, 7.37-7.26 (m, 4H), 6.99 (ddd, J = 557.1685; found, 8.2, 7.4, 1.7 Hz, 1H), 6.93 (d, J = 557.1691 5.4 Hz, 1H), 6.81 (td, J = 7.7, 1.5 Hz, 1H), 6.67 (dd, J = 8.4, 1.4 Hz, 1H), 5.76-5.69 (m, 2H), 5.37-5.26 (m, 2H), 4.67 (p, J = 7.3 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.44 (d, J = 6.4 Hz, 3H), 1.29 (d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.24, 170.28, 162.97, 160.25, 153.29, 145.68, 144.00, 142.42, 136.85, 130.30, 128.60, 128.38, 127.42, 126.92, 123.50, 121.72, 115.11, 109.53, 89.56, 81.98, 74.35, 56.17, 48.15, 20.88, 18.14, 14.93. 205 (Thin film) HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.46 3379, 2985, ([M + H]⁺) calcd for (br s, 1H), 8.29 (d, J = 5.4 Hz, 1H), 2940, 1769, C₂₇H₂₈ClN₂O₇, 7.44-7.38 (m, 2H), 7.37-7.24 (m, 1739, 1674, 527.1580; found, 4H), 7.02-6.95 (m, 2H), 6.81 (td, J = 1589, 1507, 527.1585 7.7, 1.4 Hz, 1H), 6.66 (dd, J = 8.3, 1481, 1195, 1.5 Hz, 1H), 5.36-5.25 (m, 2H), 1174, 1059, 4.66 (p, J = 7.4 Hz, 1H), 3.90 (s, 729 3H), 2.38 (s, 3H), 1.43 (d, J = 6.4 Hz, 3H), 1.27 (d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.13, 168.91, 162.39, 159.41, 153.29, 146.63, 141.46, 137.47, 136.82, 130.29, 128.59, 128.38, 127.41, 126.91, 123.50, 121.72, 115.11, 109.72, 81.96, 74.38, 56.27, 47.93, 20.76, 18.30, 14.90. 206 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.29-8.22 ([M + H]⁺) calcd for (m, 2H), 7.38-7.27 (m, 5H), C₂₈H₂₉ClFN₂O₈, 6.94 (d, J = 5.4 Hz, 1H), 6.67-6.59 575.1591; found, (m, 2H), 6.43 (dt, J = 10.5, 2.3 Hz, 575.1597 1H), 5.72 (app q, J = 6.4 Hz, 2H), 5.30-5.22 (m, 1H), 5.17 (d, J = 4.8 Hz, 1H), 4.66 (p, J = 7.3 Hz, 1H), 3.91 (s, 3H), 2.07 (s, 3H), 1.36 (d, J = 6.4 Hz, 3H), 1.30 (d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.14, 170.30, 163.09 (d, J = 248.2 Hz), 163.02, 160.28, 159.25 (d, J = 12.3 Hz), 145.67, 144.04, 142.31, 136.23, 135.22 (d, J = 13.4 Hz), 128.77, 128.60, 126.79, 112.53 (d, J = 3.3 Hz), 109.59, 109.18 (d, J = 25.2 Hz), 102.22 (d, J = 25.0 Hz), 89.54, 81.75, 73.84, 56.18, 48.18, 20.88, 18.13, 14.79. ¹⁹F NMR (471 MHz, CDCl₃) δ-109.91 (dd, J = 10.3, 8.4 Hz). 207 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.44 ([M + H]⁺) calcd for (br s, 1H), 8.29 (d, J = 5.4 Hz, 1H), C₂₇H₂₇ClFN₂O₇, 7.37-7.27 (m, 5H), 6.99 (d, J = 5.5 545.1485; found, Hz, 1H), 6.67-6.58 (m, 2H), 6.42 545.1485 (dt, J = 10.6, 2.3 Hz, 1H), 5.25 (qd, J = 6.4, 4.5 Hz, 1H), 5.15 (d, J = 4.7 Hz, 1H), 4.64 (p, J = 7.4 Hz, 1H), 3.90 (s, 3H), 2.39 (s, 3H), 1.34 (d, J = 6.4 Hz, 3H), 1.30 (d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 172.02, 168.92, 163.08 (d, J = 248.5 Hz), 162.47, 159.43, 159.23 (d, J = 12.3 Hz), 146.60, 141.33, 137.50, 136.19, 135.19 (d, J = 13.5 Hz), 128.76, 128.58, 126.79, 112.51 (d, J = 3.2 Hz), 109.79, 109.14 (d, J = 25.1 Hz), 102.20 (d, J = 25.1 Hz), 81.68, 73.86, 56.27, 48.01, 20.76, 18.23, 14.70. ¹⁹F NMR (471 MHz, CDCl₃) δ-109.96 (dd, J = 10.3, 8.5 Hz). 208 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.31 ([M + H]⁺) calcd for (d, J = 8.3 Hz, 1H), 8.25 (d, J = 5.4 C₂₉H₃₁ClFN₂O₈, Hz, 1H), 7.38-7.28 (m, 5H), 6.94 589.1747; found, (d, J = 5.4 Hz, 1H), 6.66-6.58 (m, 589.1752 2H), 6.42 (dt, J = 10.5, 2.2 Hz, 1H), 5.76-5.68 (m, 2H), 5.26 (td, J = 6.4, 4.7 Hz, 1H), 5.17 (d, J = 4.7 Hz, 1H), 4.66 (ddd, J = 8.3, 6.6, 5.2 Hz, 1H), 3.91 (s, 3H), 2.06 (s, 3H), 1.88-1.77 (m, 1H), 1.71-1.62 (m, 1H), 1.35 (d, J = 6.4 Hz, 3H), 0.79 (t, J = 7.5 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.51, 170.29, 163.08 (d, J = 248.3 Hz), 163.18, 160.31, 159.23 (d, J = 12.3 Hz), 145.68, 144.06, 142.33, 136.20, 135.22 (d, J = 13.4 Hz), 128.79, 128.60, 126.78, 112.51 (d, J = 3.2 Hz), 109.58, 109.16 (d, J = 25.2 Hz), 102.19 (d, J = 25.0 Hz), 89.59, 81.71, 73.89, 56.18, 53.34, 25.45, 20.88, 14.77, 9.34. ¹⁹F NMR (471 MHz, CDCl₃) δ-109.92 (dd, J = 10.4, 8.3 Hz). 209 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.50-8.45 ([M + H]⁺) calcd for (m, 1H), 8.30 (d, J = 5.4 Hz, C₂₈H₂₉ClFN₂O₇, 1H), 7.37-7.27 (m, 5H), 6.99 (d, J = 559.1642; found, 5.5 Hz, 1H), 6.65-6.58 (m, 2H), 559.1646 6.41 (dt, J = 10.6, 2.3 Hz, 1H), 5.25 (qd, J = 6.3, 4.4 Hz, 1H), 5.16 (d, J = 4.6 Hz, 1H), 4.67-4.59 (m, 1H), 3.90 (s, 3H), 2.39 (s, 3H), 1.87-1.77 (m, 1H), 1.71-1.61 (m, 1H), 1.33 (d, J = 6.4 Hz, 3H), 0.78 (t, J = 7.4 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.38, 168.91, 163.07 (d, J = 248.1 Hz), 162.63, 159.43, 159.21 (d, J = 12.3 Hz), 146.62, 141.38, 137.49, 136.16, 135.18 (d, J = 13.5 Hz), 128.77, 128.58, 126.77, 112.49 (d, J = 3.2 Hz), 109.77, 109.12 (d, J = 25.3 Hz), 102.16 (d, J = 25.1 Hz), 81.65, 73.89, 56.27, 53.16, 25.51, 20.76, 14.69, 9.27. ¹⁹F NMR (471 MHz, CDCl₃) δ-109.96 (dd, J = 10.3, 8.3 Hz). 210 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.54 ([M + Na]⁺) calcd for (d, J = 8.1 Hz, 1H), 8.32 (d, J = 5.4 C₂₅H₂₆N₂O₇SNa, Hz, 1H), 7.30-7.23 (m, 1H), 7.24-7.16 521.1359; found, (m, 2H), 7.06 (dd, J = 3.7, 1.2 521.1354. Hz, 1H), 7.00 (d, J = 5.5 Hz, 1H), 6.95 (dd, J = 5.0, 3.5 Hz, 1H), 6.94-6.86 (m, 3H), 5.50-5.34 (m, 2H), 4.73 (dq, J = 8.2, 7.1 Hz, 1H), 3.91 (s, 3H), 2.40 (s, 3H), 1.42 (d, J = 7.1 Hz, 3H), 1.25 (d, J = 6.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.20, 168.92, 162.40, 159.44, 157.67, 146.65, 141.54, 140.20, 137.51, 129.39, 126.74, 126.26, 125.85, 121.54, 115.99, 109.74, 78.23, 73.49, 56.28, 48.03, 20.76, 18.70, 16.04. 211 (Thin film) HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.66 3380, 2938, ([M + H]⁺) calcd for (d, J = 2.2 Hz, 1H), 8.54 (dd, J = 1770, 1509 C₂₆H₂₈N₃O₇, 4.8, 1.7 Hz, 1H), 8.44 (d, J = 7.9 Hz, 494.1936; found, 1H), 8.30 (d, J = 5.5 Hz, 1H), 7.74 494.1931 (dt, J = 7.9, 2.0 Hz, 1H), 7.24 (dd, J = 4.9, 0.8 Hz, 1H), 7.22-7.13 (m, 2H), 6.99 (d, J = 5.5 Hz, 1H), 6.91 (tt, J = 7.2, 1.1 Hz, 1H), 6.82 (dt, J = 7.8, 1.1 Hz, 2H), 5.35-5.26 (m, 1H), 5.23 (d, J = 5.4 Hz, 1H), 4.72-4.61 (m, 1H), 3.91 (s, 3H), 2.39 (s, 3H), 1.40 (d, J = 6.4 Hz, 3H), 1.27 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.99, 168.91, 162.41, 159.46, 157.31, 149.74, 148.94, 146.65, 141.39, 134.73, 133.23, 129.53, 123.58, 121.71, 116.04, 109.79, 79.29, 77.22, 73.70, 56.29, 47.86, 20.75, 18.29, 15.48. 212 (Thin film) HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.52 3376, 2928, ([M + H]⁺) calcd for (s, 1H), 8.36-8.29 (m, 1H), 7.84-7.74 1770, 1676 C₂₄H₂₆N₃O₇S, (m, 1H), 7.38-7.31 (m, 1H), 500.1483; found, 7.26-7.18 (m, 2H), 7.05-6.91 (m, 500.1478 4H), 5.67-5.56 (m, 1H), 5.58-5.47 (m, 1H), 4.78-4.67 (m, 1H), 3.91 (s, 3H), 1.44-1.34 (m, 6H). 213 (Thin film) HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 8.40-8.24 3378, 2986, ([M + H]⁺) calcd for (m, 2H), 7.80-7.77 (m, 1H), 1747, 1674 C₂₅H₂₈N₃O₈S, 7.39-7.31 (m, 1H), 7.25-7.18 (m, 530.1591; found, 2H), 7.00-6.87 (m, 4H), 5.73 (d, J = 530.1585 1.9 Hz, 2H), 5.66-5.46 (m, 2H), 4.79-4.65 (m, 1H), 3.91 (s, 3H), 2.07 (d, J = 1.8 Hz, 3H), 1.45-1.31 (m, 6H). ¹³C NMR (126 MHz, CDCl₃) δ 207.06, 170.35, 168.21, 163.00, 160.27, 157.52, 145.71, 142.76, 142.45, 129.59, 129.58, 122.13, 122.00, 120.25, 115.96, 115.60, 109.57, 89.54, 79.70, 72.94, 56.19, 53.77, 48.19, 20.88, 16.06. 214 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.53 ([M + H]⁺) calcd for (d, J = 5.5 Hz, 1H), 8.29 (d, J = 5.4 C₂₇H₂₇Cl₂N₂O₇, Hz, 1H), 7.43-7.23 (m, 6H), 7.05-6.87 561.1195; found, (m, 2H), 6.65 (d, J = 8.9 Hz, 561.1179 1H), 5.50-5.36 (m, 1H), 5.17 (d, J = 6.6 Hz, 1H), 4.79-4.65 (m, 1H), 3.89 (s, 3H), 2.39 (s, 3H), 1.41 (d, J = 7.2 Hz, 3H), 1.21 (d, J = 6.5 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.96, 168.90, 162.39, 159.45, 151.89, 146.64, 141.45, 137.51, 135.96, 130.00, 128.82, 128.75, 127.28, 127.21, 125.92, 124.14, 115.46, 109.80, 82.63, 73.24, 56.29, 48.04, 20.76, 18.53, 16.07. 215 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.47 ([M + H]⁺) calcd for (d, J = 7.9 Hz, 1H), 8.29 (d, J = 5.4 C₂₉H₃₁Cl₂N₂O₇, Hz, 1H), 7.45-7.27 (m, 6H), 7.05-6.91 589.1508; found, (m, H), 6.65 (d, J = 8.9 Hz, 589.1495 1H), 5.54-5.35 (m, 1H), 5.17 (d, J = 6.5 Hz, 1H), 4.81-4.62 (m, 1H), 3.88 (s, 3H), 3.03-2.87 (m, 1H), 1.40 (d, J = 7.2 Hz, 3H), 1.36 (d, J = 7.0 Hz, 6H), 1.21 (d, J = 6.6 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 174.71, 172.05, 162.37, 159.43, 151.90, 146.54, 141.84, 137.68, 135.96, 130.01, 128.79, 128.73, 127.28, 127.22, 125.92, 124.16, 115.46, 109.63, 82.58, 73.18, 56.30, 48.03, 33.96, 18.83, 18.57, 16.04. 216 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.36 ([M + H]⁺) calcd for (d, J = 7.9 Hz, 1H), 8.24 (d, J = 5.4 C₂₈H₂₉Cl₂N₂O₈, Hz, 1H), 7.40-7.27 (m, 6H), 7.02-6.90 591.1301; found, (m, 2H), 6.66 (d, J = 8.9 Hz, 591.1289 1H), 5.75 (s, 2H), 5.51-5.39 (m, 1H), 5.18 (d, J = 6.8 Hz, 1H), 4.84-4.63 (m, 1H), 3.91 (s, 3H), 2.07 (s, 3H), 1.44 (d, J = 7.2 Hz, 3H), 1.23 (d, J = 6.5 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.08, 170.26, 162.94, 160.28, 151.90, 145.67, 144.00, 142.38, 135.99, 129.99, 128.84, 128.77, 127.28, 127.20, 125.91, 124.11, 115.43, 109.59, 89.53, 82.75, 73.26, 56.19, 48.25, 20.87, 18.41, 16.13. 217 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.53 ([M + H]⁺) calcd for (d, J = 7.0 Hz, 1H), 8.30 (d, J = 5.4 C₂₇H₂₉N₂O₇, Hz, 1H), 7.43-7.35 (m, 2H), 7.34-7.23 493.1975; found, (m, 3H), 7.21-7.08 (m, 2H), 493.1969 6.98 (d, J = 5.5 Hz, 1H), 6.91-6.74 (m, 3H), 5.50-5.32 (m, 1H), 5.12 (d, J = 6.4 Hz, 1H), 4.79-4.62 (m, 1H), 3.88 (s, 3H), 2.39 (s, 3H), 1.37 (d, J = 7.1 Hz, 3H), 1.21 (d, J = 6.5 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.24, 168.92, 162.40, 159.45, 157.85, 146.69, 141.54, 137.50, 137.36, 129.35, 128.60, 128.36, 127.18, 121.05, 115.79, 109.78, 81.81, 73.75, 56.29, 48.03, 20.77, 18.71, 16.27. 218 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) 8.47 ([M + H]⁺) calcd for (d, J = 6.6 Hz, 1H), 8.29 (d, J = 5.4 C₂₉H₃₃N₂O₇, Hz, 1H), 7.41-7.35 (m, 2H), 7.35-7.21 521.2288; found, (m, 3H), 7.19-7.11 (m, 2H), 521.2285 6.96 (d, J = 5.5 Hz, 1H), 6.91-6.72 (m, 3H), 5.49-5.28 (m, 1H), 5.12 (d, J = 6.4 Hz, 1H), 4.80-4.60 (m, 1H), 3.86 (s, 3H), 3.09-2.82 (m, 1H), 1.41-1.32 (m, 9H), 1.21 (d, J = 6.5 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 174.72, 172.32, 162.39, 159.42, 157.86, 146.59, 141.93, 137.66, 137.37, 129.34, 128.59, 128.34, 127.18, 121.04, 115.79, 109.63, 81.78, 73.70, 56.29, 48.02, 33.96, 18.83, 18.74, 16.25. 219 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.35 ([M + H]⁺) calcd for (d, J = 7.9 Hz, 1H), 8.26 (d, J = 5.4 C₂₈H₃₁N₂O₈, Hz, 1H), 7.45-7.36 (m, 2H), 7.36-7.22 523.2080; found, (m, 3H), 7.21-7.09 (m, 2H), 523.2081 6.94 (d, J = 5.4 Hz, 1H), 6.91-6.75 (m, 3H), 5.74 (s, 2H), 5.48-5.34 (m, 1H), 5.13 (d, J = 6.5 Hz, 1H), 4.82-4.64 (m, 1H), 3.89 (s, 3H), 2.06 (s, 3H), 1.39 (d, J = 7.2 Hz, 3H), 1.23 (d, J = 6.5 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.36, 170.28, 162.97, 160.27, 157.86, 145.72, 143.98, 142.50, 137.38, 129.34, 128.61, 128.36, 127.16, 121.04, 115.78, 109.59, 89.54, 81.87, 73.76, 56.19, 48.25, 20.88, 18.55, 16.32. 220 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.26 ([M + H]⁺) calcd for (t, J = 7.2 Hz, 2H), 7.60-7.56 (m, C₃₂H₃₇N₂O₈, 3H), 7.52-7.49 (m, 1H), 7.46-7.31 577.2544; found, (m, 6H), 6.92 (d, J = 5.4 Hz, 1H), 577.2557. 5.72 (s, 2H), 5.18 (p, J = 6.4 Hz, 1H), 4.61 (p, J = 7.2 Hz, 1H), 4.42 (d, J = 6.4 Hz, 1H), 3.89 (s, 3H), 3.24 (d, J = 6.7 Hz, 2H), 2.05 (s, 3H), 1.38 (d, J = 6.3 Hz, 3H), 1.16 (d, J = 7.2 Hz, 3H), 1.08-1.00 (m, 1H), 0.55-0.43 (m, 2H), 0.19-0.08 (m, 2H). ¹³C NMR (101 MHz, CDCl₃) δ 172.11, 170.26, 162.89, 160.25, 145.68, 143.97, 142.50, 141.19, 140.88, 139.47, 128.79, 128.72, 127.38, 127.11, 126.76, 126.50, 126.32, 109.51, 89.57, 83.15, 74.28, 73.90, 56.16, 48.09, 20.86, 18.09, 16.03, 10.63, 3.22, 2.75. 221 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.28 ([M + H]⁺) calcd for (d, J = 7.8 Hz, 1H), 8.24 (d, J = 5.4 C₃₄H₃₄FN₂O₈, Hz, 1H), 7.60 (s, 1H), 7.57-7.51 617.2294; found, (m, 3H), 7.46-7.40 (m, 3H), 7.39-7.34 617.2312. (m, 2H), 7.11 (dd, J = 15.1, 8.2 Hz, 1H), 6.93 (d, J = 5.4 Hz, 1H), 6.66-6.56 (m, 3H), 5.74-5.69 (m, 2H), 5.32 (dd, J = 6.3, 5.0 Hz, 1H), 5.27 (d, J = 4.9 Hz, 1H), 4.67 (p, J = 7.2 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.42 (d, J = 6.4 Hz, 3H), 1.26 (d, J = 7.1 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.27, 170.27, 163.00, 160.27, 145.67, 144.03, 142.36, 141.66, 140.58, 137.63, 130.21, 130.11, 129.12, 128.83, 127.55, 127.14, 125.76, 125.51, 111.56, 109.56, 108.25, 108.04, 103.94, 103.69, 56.17, 48.16, 20.87, 18.11, 14.86. ¹⁹F NMR (376 MHz, CDCl₃) δ-111.52. 222 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.45 ([M + H]⁺) calcd for (s, 1H), 8.30 (d, J = 5.4 Hz, 1H), C₃₁H₃₅N₂O₇, 7.60-7.55 (m, 3H), 7.52-7.48 (m, 547.2439; found, 1H), 7.47-7.30 (m, 5H), 6.98 (d, J = 547.2447. 5.5 Hz, 1H), 5.17 (p, J = 6.4 Hz, 1H), 4.64-4.55 (m, 1H), 4.41 (d, J = 6.3 Hz, 1H), 3.89 (s, 3H), 3.24 (d, J = 6.8 Hz, 2H), 2.38 (s, 3H), 1.37 (d, J = 6.3 Hz, 3H), 1.14 (d, J = 7.2 Hz, 3H), 1.03 (tdd, J = 8.0, 7.4, 1.9 Hz, 1H), 0.55-0.43 (m, 2H), 0.19-0.07 (m, 2H). ¹³C NMR (101 MHz, CDCl₃) δ 172.00, 168.89, 162.30, 159.41, 146.63, 141.53, 141.19, 140.88, 139.45, 128.79, 128.72, 127.37, 127.12, 126.75, 126.46, 126.31, 109.69, 83.11, 74.34, 73.91, 56.26, 47.88, 20.75, 18.27, 15.96, 10.63, 3.21, 2.75. 223 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.45 ([M + H]⁺) calcd for (s, 1H), 8.28 (d, J = 5.4 Hz, 1H), C₃₃H₃₂FN₂O₇, 7.59 (s, 1H), 7.57-7.50 (m, 3H), 587.2188; found, 7.46-7.34 (m, 5H), 7.11 (dd, J = 587.2196. 15.2, 8.2 Hz, 1H), 6.98 (d, J = 5.5 Hz, 1H), 6.66-6.55 (m, 3H), 5.32 (dd, J = 8.8, 3.9 Hz, 1H), 5.26 (d, J = 4.8 Hz, 1H), 4.65 (p, J = 7.3 Hz, 1H), 3.90 (s, 3H), 2.38 (s, 3H), 1.40 (d, J = 6.3 Hz, 3H), 1.25 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.16, 168.90, 162.44, 159.43, 146.62, 141.65, 141.40, 140.58, 137.61, 130.19, 130.09, 129.12, 128.82, 127.54, 127.18, 127.15, 125.75, 125.51, 111.60, 111.57, 109.75, 108.23, 104.03, 103.93, 103.69, 81.59, 74.21, 56.27, 47.95, 20.75, 18.25, 14.83. 224 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.55 ([M + H]⁺) calcd for (d, J = 5.9 Hz, 1H), 8.33 (d, J = 5.4 C₂₅H₃₃N₂O₇, Hz, 1H), 7.38-7.22 (m, 5H), 7.00 473.2288; found, (d, J = 5.5 Hz, 1H), 5.25-5.11 (m, 473.2290 1H), 4.82-4.63 (m, 1H), 4.24 (d, J = 6.7 Hz, 1H), 3.89 (s, 3H), 3.14-2.97 (m, 2H), 2.40 (s, 3H), 1.46 (d, J = 7.2 Hz, 3H), 1.07 (d, J = 6.5 Hz, 3H), 0.90-0.81 (m, 6H). ¹³C NMR (101 MHz, CDCl₃) δ 172.17, 168.89, 162.34, 159.44, 146.67, 146.65, 141.61, 138.52, 137.48, 128.27, 128.04, 127.66, 109.75, 83.96, 76.05, 74.13, 56.28, 48.06, 28.62, 20.76, 19.41, 19.36, 18.75, 16.27. 225 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.46 ([M + H]⁺) calcd for (d, J = 7.9 Hz, 1H), 8.31 (d, J = 5.4 C₂₅H₃₃N₂O₇, Hz, 1H), 7.35-7.18 (m, 5H), 6.99 473.2288; found, (d, J = 5.4 Hz, 1H), 5.18-5.01 (m, 473.2288 1H), 4.70-4.52 (m, 1H), 4.35-4.14 (m, 1H), 3.88 (d, J = 1.6 Hz, 3H), 3.19-3.10 (m, 1H), 3.09-3.00 (m, 1H), 2.38 (d, J = 1.4 Hz, 3H), 1.30 (d, J = 6.5, 3H), 1.19 (d, J = 7.1 Hz, 3H), 0.93-0.80 (m, 6H). ¹³C NMR (101 MHz, CDCl₃) δ 171.96, 168.88, 162.31, 159.43, 146.65, 141.53, 138.89, 137.46, 128.18, 127.89, 127.53, 109.75, 83.70, 76.28, 74.48, 56.27, 47.89, 28.64, 20.74, 19.36, 19.34, 18.32, 15.79. 226 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.37 ([M + H]⁺) calcd for (d, J = 7.8 Hz, 1H), 8.28 (d, J = 5.4 C₂₆H₃₅N₂O₈, Hz, 1H), 7.43-7.25 (m, 5H), 6.96 503.2393; found, (d, J = 5.4 Hz, 1H), 5.75 (s, 2H), 503.2401 5.19 (p, J = 6.5 Hz, 1H), 4.74 (p, J = 7.2 Hz, 1H), 4.25 (d, J = 6.7 Hz, 1H), 3.91 (s, 3H), 3.17-2.97 (m, 2H), 2.07 (s, 3H), 1.48 (d, J = 7.1 Hz, 3H), 1.09 (d, J = 6.5 Hz, 3H), 0.92-0.81 (m, 6H). ¹³C NMR (101 MHz, CDCl₃) δ 172.29, 170.26, 162.92, 160.26, 145.72, 143.94, 142.61, 138.53, 128.27, 128.05, 127.65, 109.55, 89.54, 84.01, 76.06, 74.13, 56.18, 48.27, 28.62, 20.86, 19.40, 19.36, 18.60, 16.32. 227 (Thin film) HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.55 3381, 2963, ([M + H]⁺) calcd for (d, J = 7.7 Hz, 1H), 8.34 (d, J = 5.5 2876, 1676 C₂₄H₃₁N₂O₇, Hz, 1H), 7.41-7.27 (m, 5H), 7.00 459.2131; found, (d, J = 5.5 Hz, 1H), 5.24-5.11 (m, 459.2124. 1H), 4.78-4.65 (m, 1H), 4.25 (d, J = 6.8 Hz, 1H), 3.91 (s, 3H), 3.29 (dt, J = 9.1, 6.8 Hz, 1H), 3.23 (dt, J = 9.1, 6.5 Hz, 1H), 2.40 (s, 3H), 1.59-1.49 (m, 2H), 1.46 (d, J = 7.2 Hz, 3H), 1.07 (d, J = 6.5 Hz, 3H), 0.87 (t, J = 7.3 Hz, 3H). 228 (Thin film) HRMS-FAB (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.46 3379, 2963, ([M + H]⁺) calcd for (s, 1H), 8.32 (d, J = 5.4 Hz, 1H), 2937, 1771 C₂₄H₃₁N₂O₇, 7.36-7.27 (m, 5H), 6.99 (d, J = 5.5 459.2131; found, Hz, 1H), 5.10 (p, J = 6.3 Hz, 1H), 459.2125. 4.60 (dq, J = 8.2, 7.2 Hz, 1H), 4.27 (d, J = 6.1 Hz, 1H), 3.90 (s, 3H), 3.33 (dt, J = 9.1, 6.6 Hz, 1H), 3.25 (dt, J = 9.1, 6.5 Hz, 1H), 2.39 (s, 3H), 1.60-1.50 (m, 2H), 1.30 (d, J = 6.3 Hz, 3H), 1.18 (d, J = 7.1 Hz, 3H), 0.89 (t, J = 7.4 Hz, 3H). 229 (Thin film) HRMS-FAB (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.56 3379, 2984, ([M + H]⁺) calcd for (d, J = 7.8 Hz, 1H), 8.33 (d, J = 5.4 2939, 1770 C₂₂H₂₇N₂O₇, Hz, 1H), 7.40-7.26 (m, 5H), 7.00 431.1818; found, (d, J = 5.5 Hz, 1H), 5.27-5.14 (m, 431.1818. 1H), 4.83-4.66 (m, 1H), 4.14 (d, J = 6.9 Hz, 1H), 3.90 (s, 3H), 3.23 (s, 3H), 2.40 (s, 3H), 1.47 (d, J = 7.1 Hz, 3H), 1.08 (d, J = 6.5 Hz, 3H). 230 (Thin film) HRMS-FAB (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.37 3377, 2985, ([M + H]⁺) calcd for (d, J = 7.8 Hz, 1H), 8.28 (d, J = 5.3 2938, 1740 C₂₃H₂₉N₂O₈, Hz, 1H), 7.39-7.27 (m, 5H), 6.95 461.1924; found, (d, J = 5.4 Hz, 1H), 5.75 (s, 2H), 461.1922. 5.28-5.15 (m, 1H), 4.75 (p, J = 7.2 Hz, 1H), 4.14 (d, J = 6.9 Hz, 1H), 3.91 (s, 3H), 3.24 (s, 3H), 2.07 (s, 3H), 1.49 (d, J = 7.2 Hz, 3H), 1.10 (d, J = 6.5 Hz, 3H). 231 (Thin film) HRMS-FAB (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.46 3377, 2984, ([M + H]⁺) calcd for (d, J = 7.1 Hz, 1H), 8.32 (d, J = 5.5 1770, 1675 C₂₂H₂₇N₂O₇, Hz, 1H), 7.39-7.26 (m, 5H), 6.99 431.1818; found, (d, J = 5.5 Hz, 1H), 5.17-4.99 (m, 431.1808. 1H), 4.60 (dq, J = 8.1, 7.1 Hz, 1H), 4.18 (d, J = 5.9 Hz, 1H), 3.90 (s, 3H), 3.26 (s, 3H), 2.39 (s, 3H), 1.29 (d, J = 6.4 Hz, 3H), 1.20 (d, J = 7.2 Hz, 3H). 232 (Thin film) HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.56 3378, 2986, ([M + H]⁺) calcd for (d, J = 7.9 Hz, 1H), 8.33 (d, J = 5.5 1771, 1676 C₂₅H₃₁N₂O₇, Hz, 1H), 7.37-7.28 (m, 5H), 7.00 471.2131; found, (d, J = 5.5 Hz, 1H), 5.25-5.13 (m, 471.2123. 1H), 4.80-4.67 (m, 1H), 4.32 (d, J = 6.8 Hz, 1H), 3.90 (s, 3H), 3.16 (dd, J = 6.8, 1.2 Hz, 2H), 2.40 (s, 3H), 1.48 (d, J = 7.2 Hz, 3H), 1.08 (d, J = 6.5 Hz, 3H), 1.04-0.94 (m, 1H), 0.53-0.39 (m, 2H), 0.17-0.02 (m, 2H). 233 (Thin film) HRMS-FAB (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.53-8.40 3385, 2986, ([M + H]⁺) calcd for (m, 1H), 8.32 (d, J = 5.5 Hz, 1771, 1676 C₂₅H₃₁N₂O₇, 1H), 7.36-7.27 (m, 5H), 6.99 (d, J = 471.2131; found, 5.5 Hz, 1H), 5.20-5.05 (m, 1H), 471.2126. 4.71-4.48 (m, 1H), 4.33 (d, J = 6.3 Hz, 1H), 3.90 (s, 3H), 3.19 (dd, J = 6.8, 1.3 Hz, 2H), 2.39 (s, 3H), 1.33 (d, J = 6.3 Hz, 3H), 1.16 (d, J = 7.2 Hz, 3H), 1.06-0.90 (m, 1H), 0.53-0.38 (m, 2H), 0.22-0.04 (m, 2H). 234 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.26 ([M + H]⁺) calcd for (t, J = 7.7 Hz, 2H), 7.59-7.51 (m, C₃₂H₃₇N₂O₈, 4H), 7.46-7.38 (m, 4H), 7.34 (dd, J = 577.2544; found, 8.3, 6.3 Hz, 1H), 6.92 (d, J = 5.5 577.2553. Hz, 1H), 5.73 (s, 2H), 5.17 (p, J = 6.3 Hz, 1H), 4.63 (dd, J = 14.8, 7.3 Hz, 1H), 4.39 (d, J = 6.2 Hz, 1H), 3.89 (s, 3H), 3.24 (d, J = 6.8 Hz, 2H), 2.06 (s, 3H), 1.37 (d, J = 6.3 Hz, 3H), 1.21 (d, J = 7.2 Hz, 3H), 1.04 (tdd, J = 8.0, 7.4, 2.5 Hz, 1H), 0.55-0.43 (m, 2H), 0.20-0.09 (m, 2H). ¹³C NMR (101 MHz, CDCl₃) δ 172.08, 170.27, 162.89, 160.26, 145.68, 143.98, 142.53, 140.86, 140.76, 137.84, 128.75, 128.03, 127.31, 127.06, 126.95, 109.51, 89.57, 82.83, 74.25, 73.85, 56.16, 48.11, 20.87, 18.17, 16.03, 10.62, 3.21, 2.74. 235 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.45 ([M + H]⁺) calcd for (d, J = 6.4 Hz, 1H), 8.29 (d, J = 5.4 C₂₇H₂₈FN₂O₇, Hz, 1H), 7.43-7.27 (m, 5H), 6.98 511.1880; found, (d, J = 5.5 Hz, 1H), 6.92-6.80 (m, 511.1879 2H), 6.81-6.66 (m, 2H), 5.26 (qd, J = 6.5, 5.0 Hz, 1H), 5.11 (d, J = 4.9 Hz, 1H), 4.65 (dq, J = 8.1, 7.2 Hz, 1H), 3.90 (s, 3H), 2.39 (s, 3H), 1.36 (d, J = 6.4 Hz, 3H), 1.26 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-123.24. 236 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.49 ([M + H]⁺) calcd for (d, J = 7.9 Hz, 1H), 8.31 (d, J = 5.4 C₂₇H₂₇F₂N₂O₇, Hz, 1H), 7.38-7.28 (m, 2H), 7.09-6.93 529.1786; found, (m, 3H), 6.92-6.79 (m, 2H), 529.1788 6.79-6.64 (m, 2H), 5.40-5.28 (m, 1H), 5.03 (d, J = 6.5 Hz, 1H), 4.72 (dq, J = 8.2, 7.2 Hz, 1H), 3.92 (s, 3H), 2.40 (s, 3H), 1.40 (d, J = 7.2 Hz, 3H), 1.19 (d, J = 6.5 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-113.21, −123.09. 237 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.27 ([M + H]⁺) calcd for (d, J = 5.1 Hz, 1H), 8.25 (d, J = 5.5 C₂₈H₃₀FN₂O₈, Hz, 1H), 7.45-7.25 (m, 5H), 6.93 541.1986; found, (d, J = 5.5 Hz, 1H), 6.90-6.80 (m, 541.1992 2H), 6.80-6.68 (m, 2H), 5.78-5.61 (m, 2H), 5.27 (qd, J = 6.4, 4.9 Hz, 1H), 5.12 (d, J = 4.9 Hz, 1H), 4.66 (p, J = 7.2 Hz, 1H), 3.91 (s, 3H), 2.07 (s, 3H), 1.38 (d, J = 6.4 Hz, 3H), 1.27 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-123.22. 238 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.32 ([M + H]⁺) calcd for (d, J = 7.9 Hz, 1H), 8.26 (d, J = 4.9 C₂₈H₂₉F₂N₂O₈, Hz, 1H), 7.40-7.30 (m, 2H), 7.04-6.98 559.1892; found, (m, 2H), 6.95 (d, J = 5.1 Hz, 559.1889 1H), 6.90-6.81 (m, 2H), 6.78-6.71 (m, 2H), 5.74 (s, 2H), 5.42-5.29 (m, 1H), 5.03 (d, J = 6.5 Hz, 1H), 4.82-4.70 (m, 1H), 3.92 (s, 3H), 2.07 (s, 3H), 1.42 (d, J = 7.2 Hz, 3H), 1.20 (d, J = 6.5 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-113.16, −123.06. double check 239 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.28 ([M + H]⁺) calcd for (d, J = 7.8 Hz, 1H), 8.24 (d, J = 5.4 C₃₄H₃₅N₂O₈, Hz, 1H), 7.57-7.52 (m, 4H), 7.49-7.39 599.2388; found, (m, 4H), 7.34 (dd, J = 8.3, 6.3 599.2395. Hz, 1H), 7.19 (dd, J = 8.6, 7.4 Hz, 2H), 6.93-6.85 (m, 4H), 5.72 (t, J = 3.6 Hz, 2H), 5.35-5.29 (m, 1H), 5.26 (d, J = 5.0 Hz, 1H), 4.69 (p, J = 7.2 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.42 (d, J = 6.4 Hz, 3H), 1.28 (d, J = 7.2 Hz, 3H). 240 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.28 ([M + H]⁺) calcd for (d, J = 7.8 Hz, 1H), 8.24 (d, J = 5.4 C₃₄H₃₅N₂O₈, Hz, 1H), 7.63 (s, 1H), 7.56 (dd, J = 599.2388; found, 5.1, 3.4 Hz, 2H), 7.52-7.49 (m, 599.2393. 1H), 7.45-7.38 (m, 4H), 7.35 (ddd, J = 7.3, 3.8, 1.2 Hz, 1H), 7.21-7.15 (m, 2H), 6.93-6.86 (m, 4H), 5.74-5.70 (m, 2H), 5.37-5.30 (m, 1H), 5.29 (d, J = 1.8 Hz, 1H), 4.67 (p, J = 7.2 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.43 (d, J = 6.3 Hz, 3H), 1.23 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.31, 170.28, 162.98, 160.27, 157.97, 145.69, 144.01, 142.43, 141.50, 140.69, 138.29, 129.39, 129.01, 128.80, 127.48, 127.14, 126.97, 125.88, 125.65, 121.26, 116.06, 109.54, 89.57, 81.39, 74.40, 56.17, 48.14, 20.87, 18.13, 15.05. 241 ESIMS m/z 541 ¹H NMR (400 MHz, CDCl₃) δ 8.26 ([M + H]⁺) (t, J = 6.2 Hz, 2H), 7.40-7.35 (m, 2H), 7.17 (dd, J = 8.4, 7.6 Hz, 2H), 7.01 (t, J = 8.6 Hz, 2H), 6.94 (d, J = 5.4 Hz, 1H), 6.89 (t, J = 7.3 Hz, 1H), 6.83-6.79 (m, 2H), 5.74-5.70 (m, 2H), 5.29-5.22 (m, 1H), 5.18 (d, J = 5.3 Hz, 1H), 4.66 (p, J = 7.2 Hz, 1H), 3.91 (s, 3H), 2.06 (s, 3H), 1.39 (d, J = 6.4 Hz, 3H), 1.28 (d, J = 7.2 Hz, 3H). ¹³C NMR (151 MHz, CDCl₃) δ 172.16, 170.29, 163.30, 162.97, 161.67, 160.29, 157.64, 145.70, 144.04, 142.39, 133.40, 133.38, 129.40, 128.76, 128.71, 121.37, 116.00, 115.59, 115.44, 109.59, 89.56, 80.67, 74.11, 56.19, 48.13, 20.88, 18.20, 15.23. 242 ESIMS m/z 511 ¹H NMR (400 MHz, CDCl₃) δ 8.45 ([M + H]⁺) (d, J = 6.7 Hz, 1H), 8.29 (d, J = 5.4 Hz, 1H), 7.40-7.33 (m, 2H), 7.20-7.14 (m, 2H), 7.03-6.97 (m, 3H), 6.89 (t, J = 7.4 Hz, 1H), 6.83-6.78 (m, 2H), 5.28-5.21 (m, 1H), 5.17 (d, J = 5.2 Hz, 1H), 4.65 (dq, J = 14.5, 7.2 Hz, 1H), 3.90 (s, 3H), 2.39 (s, 3H), 1.37 (d, J = 6.4 Hz, 3H), 1.27 (d, J = 7.2 Hz, 3H). ¹³C NMR (151 MHz, CDCl₃) δ 172.04, 168.91, 163.30, 162.40, 161.67, 159.47, 157.64, 146.66, 141.43, 137.52, 133.36, 133.34, 129.40, 128.77, 128.72, 121.37, 116.01, 115.58, 115.44, 109.81, 80.64, 74.12, 56.30, 47.90, 20.76, 15.24. 243 HRMS-ESI (m/z) ¹H NMR (300 MHz, CDCl₃) δ 8.47 ([M + H]⁺) calcd for (d, J = 8.0 Hz, 1H), 8.29 (d, J = 5.4 C₂₈H₃₀ClN₂O₇, Hz, 1H), 7.43-7.36 (m, 2H), 7.36-7.22 541.1741; found, (m, 3H), 7.13 (dd, J = 2.2, 0.8 541.1733 Hz, 1H), 6.97 (d, J = 5.5 Hz, 1H), 6.77 (ddd, J = 8.4, 2.2, 0.9 Hz, 1H), 6.55 (d, J = 8.4 Hz, 1H), 5.41-5.24 (m, 1H), 5.22 (d, J = 4.8 Hz, 1H), 4.65 (dq, J = 8.3, 7.2 Hz, 1H), 3.88 (s, 3H), 2.38 (s, 3H), 2.18 (s, 3H), 1.42 (d, J = 6.4 Hz, 3H), 1.27 (d, J = 7.2 Hz, 3H). ¹³C NMR (75 MHz, CDCl₃) δ 172.15, 168.93, 162.40, 159.41, 151.06, 146.67, 141.44, 137.46, 137.01, 131.47, 130.71, 128.55, 128.33, 127.85, 126.99, 123.08, 115.10, 109.76, 82.07, 74.36, 56.30, 47.94, 20.77, 20.23, 18.32, 15.00. 244 HRMS-ESI (m/z) ¹H NMR (300 MHz, CDCl₃) δ 8.28 ([M + H]⁺) calcd for (d, J = 8.8 Hz, 1H), 8.25 (d, J = 5.4 C₂₉H₃₂ClN₂O₈, Hz, 1H), 7.45-7.37 (m, 2H), 7.37-7.22 571.1847; found, (m, 3H), 7.13 (dd, J = 2.1, 0.8 571.1834 Hz, 1H), 6.93 (d, J = 5.4 Hz, 1H), 6.77 (ddd, J = 8.3, 2.2, 0.8 Hz, 1H), 6.56 (d, J = 8.3 Hz, 1H), 5.72 (d, J = 1.4 Hz, 2H), 5.33 (qd, J = 6.4, 4.0 Hz, 1H), 5.23 (d, J = 4.9 Hz, 1H), 4.78-4.58 (m, 1H), 3.90 (s, 3H), 2.18 (s, 3H), 2.06 (s, 3H), 1.43 (d, J = 6.4 Hz, 3H), 1.28 (d, J = 7.2 Hz, 3H). ¹³C NMR (75 MHz, CDCl₃) δ 172.24, 170.29, 162.97, 160.25, 151.05, 145.71, 143.97, 142.42, 137.03, 131.48, 130.71, 128.54, 128.32, 127.84, 127.00, 123.07, 115.09, 109.56, 89.54, 82.08, 74.32, 56.20, 48.16, 20.90, 20.23, 18.14, 15.02. 245 HRMS-ESI (m/z) ¹H NMR (300 MHz, CDCl₃) δ 8.32-8.24 ([M + H]⁺) calcd for (m, 2H), 7.48-7.34 (m, 2H), C₂₉H₃₁ClFN₂O₈, 7.13 (dd, J = 2.1, 0.8 Hz, 1H), 7.07-6.98 589.1753; found, (m, 2H), 6.94 (d, J = 5.4 Hz, 589.1746 1H), 6.79 (ddd, J = 8.4, 2.2, 0.9 Hz, 1H), 6.54 (d, J = 8.3 Hz, 1H), 5.72 (d, J = 0.9 Hz, 2H), 5.31 (qd, J = 6.4, 5.0 Hz, 1H), 5.21 (d, J = 5.0 Hz, 1H), 4.80-4.56 (m, 1H), 3.90 (s, 3H), 2.19 (s, 3H), 2.06 (s, 3H), 1.43 (d, J = 6.4 Hz, 3H), 1.30 (d, J = 7.2 Hz, 3H). ¹³C NMR (75 MHz, CDCl₃) δ 172.17, 170.29, 162.98, 162.56 (d, J = 247.0 Hz), 160.26, 150.79, 145.71, 143.98, 142.36, 132.80 (d, J = 3.2 Hz), 131.77, 130.79, 128.81 (d, J = 8.2 Hz), 127.86, 123.20, 115.53 (d, J = 21.6 Hz), 115.22, 109.59, 89.51, 81.53, 74.08, 56.18 (d, J = 3.1 Hz), 48.13, 20.87 (d, J = 2.1 Hz), 20.24 (d, J = 1.8 Hz), 18.14, 15.15. 246 HRMS-ESI (m/z) ¹H NMR (300 MHz, CDCl₃) δ 8.48 ([M + H]⁺) calcd for (d, J = 7.9 Hz, 1H), 8.27 (d, J = 5.4 C₂₈H₃₁N₂O₇, Hz, 1H), 7.44-7.35 (m, 2H), 7.35-7.18 507.2131; found, (m, 3H), 6.99-6.90 (m, 3H), 507.2120 6.79-6.68 (m, 2H), 5.27 (qd, J = 6.4, 5.0 Hz, 1H), 5.15 (d, J = 5.2 Hz, 1H), 4.65 (dq, J = 8.1, 7.1 Hz, 1H), 3.86 (s, 3H), 2.38 (s, 3H), 2.20 (s, 3H), 1.37 (d, J = 6.5 Hz, 3H), 1.24 (d, J = 7.2 Hz, 3H). ¹³C NMR (75 MHz, CDCl₃) δ 172.13, 168.93, 162.40, 159.44, 155.77, 146.69, 141.44, 137.75, 137.48, 130.41, 129.80, 128.49, 128.12, 127.04, 115.88, 109.80, 81.40, 74.34, 56.29, 47.93, 20.78, 20.46, 18.38, 15.16. 247 HRMS-ESI (m/z) ¹H NMR (300 MHz, CDCl₃) δ 8.46 ([M + H]⁺) calcd for (d, J = 8.2 Hz, 1H), 8.28 (d, J = 5.4 C₂₈H₃₀FN₂O₇, Hz, 1H), 7.45-7.30 (m, 2H), 7.06-6.91 525.2037; found, (m, 5H), 6.76-6.63 (m, 2H), 525.2021 5.24 (qd, J = 6.4, 5.2 Hz, 1H), 5.12 (d, J = 5.3 Hz, 1H), 4.65 (dq, J = 8.3, 7.2 Hz, 1H), 3.88 (s, 3H), 2.39 (s, 3H), 2.21 (s, 3H), 1.37 (d, J = 6.3 Hz, 3H), 1.27 (d, J = 7.1 Hz, 3H). ¹³C NMR (75 MHz, CDCl₃) δ 172.04, 168.93, 162.44 (d, J = 246.6 Hz), 162.40, 159.45, 155.49, 146.68, 141.39, 137.50, 133.52 (d, J = 3.2 Hz), 130.63, 129.84, 128.78 (d, J = 8.2 Hz), 115.88, 115.46 (d, J = 21.5 Hz), 109.82, 80.79, 74.12, 56.28 (d, J = 1.9 Hz), 47.89, 20.77 (d, J = 1.5 Hz), 20.45 (d, J = 1.8 Hz), 18.37, 15.29. 248 HRMS-ESI (m/z) ¹H NMR (300 MHz, CDCl₃) δ 8.29 ([M + H]⁺) calcd for (d, J = 8.5 Hz, 1H), 8.24 (d, J = 5.4 C₂₉H₃₃N₂O₈, Hz, 1H), 7.46-7.35 (m, 2H), 7.35-7.18 537.2237; found, (m, 3H), 6.99-6.88 (m, 3H), 537.2229 6.80-6.66 (m, 2H), 5.72 (d, J = 1.6 Hz, 2H), 5.27 (qd, J = 6.4, 4.9 Hz, 1H), 5.16 (d, J = 5.1 Hz, 1H), 4.75-4.57 (m, 1H), 3.88 (s, 3H), 2.20 (s, 3H), 2.06 (s, 3H), 1.39 (d, J = 6.4 Hz, 3H), 1.26 (d, J = 7.2 Hz, 3H). ¹³C NMR (75 MHz, CDCl₃) δ 172.23, 170.29, 162.97, 160.27, 155.76, 145.72, 143.97, 142.40, 137.77, 130.40, 129.79, 128.48, 128.09, 127.02, 115.85, 109.60, 89.52, 81.40, 74.30, 56.20, 56.17, 48.15, 20.88 (d, J = 2.0 Hz), 20.44 (d, J = 1.8 Hz), 18.18, 15.15.z 249 HRMS-ESI (m/z) ¹H NMR (300 MHz, CDCl₃) δ 8.28 ([M + H]⁺) calcd for (d, J = 7.9 Hz, 1H), 8.25 (d, J = 5.4 C₂₉H₃₂FN₂O₈, Hz, 1H), 7.45-7.31 (m, 2H), 7.08-6.86 555.2142; found, (m, 5H), 6.77-6.65 (m, 2H), 555.2133 5.73 (d, J = 1.0 Hz, 2H), 5.33-5.19 (m, 1H), 5.13 (d, J = 5.3 Hz, 1H), 4.76-4.51 (m, 1H), 3.90 (s, 3H), 2.21 (s, 3H), 2.06 (s, 3H), 1.38 (d, J = 6.3 Hz, 3H), 1.28 (d, J = 7.2 Hz, 3H). ¹³C NMR (75 MHz, CDCl₃) δ 172.15, 170.29, 162.97, 162.43 (d, J = 246.6 Hz), 160.28, 155.49, 145.72, 143.99, 142.35, 133.54 (d, J = 3.2 Hz), 130.63, 129.83, 128.77 (d, J = 8.2 Hz), 115.86, 115.45 (d, J = 21.6 Hz), 109.62, 89.50, 80.80, 74.09, 56.19 (d, J = 2.6 Hz), 48.12, 20.87 (d, J = 2.2 Hz), 20.44 (d, J = 1.9 Hz), 18.19, 15.27. 250 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.28 ([M + H]⁺) calcd for (d, J = 7.8 Hz, 1H), 8.25 (dd, J = C₂₈H₂₉F₂N₂O₈, 5.4, 1.0 Hz, 1H), 7.44 (dt, J = 14.6, 559.1886; found, 7.3 Hz, 1H), 7.20 (t, J = 7.7 Hz, 559.1883. 2H), 6.96-6.88 (m, 2H), 6.86-6.77 (m, 4H), 5.77-5.69 (m, 2H), 5.49 (d, J = 5.7 Hz, 1H), 5.37 (p, J = 6.2 Hz, 1H), 4.69 (p, J = 7.3 Hz, 1H), 3.90 (d, J = 0.9 Hz, 3H), 2.06 (s, 3H), 1.40 (d, J = 6.4 Hz, 3H), 1.31 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.94, 170.27, 162.93, 160.28, 157.09, 145.67, 144.03, 142.39, 129.68 (dd, J = 14.7, 10.2 Hz), 129.52, 121.60, 120.60 (d, J = 7.0 Hz), 115.58, 112.00 (d, J = 21.2 Hz), 109.58, 103.61 (t, J = 25.6 Hz), 89.54, 74.01, 72.91, 56.18, 48.10, 20.86, 18.17, 15.96. ¹⁹F NMR (376 MHz, CDCl₃) δ-109.61 (d, J = 7.6 Hz), −113.91 (d, J = 7.6 Hz). 251 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.46 ([M + H]⁺) calcd for (d, J = 6.2 Hz, 1H), 8.30 (d, J = 5.4 C₂₇H₂₇F₂N₂O₇, Hz, 1H), 7.44 (dt, J = 14.6, 7.2 Hz, 529.1781; found, 1H), 7.23-7.16 (m, 2H), 6.99 (d, J = 529.1777. 5.5 Hz, 1H), 6.90 (dd, J = 9.7, 5.0 Hz, 1H), 6.83-6.77 (m, 4H), 5.48 (d, J = 5.7 Hz, 1H), 5.36 (p, J = 6.3 Hz, 1H), 4.67 (p, J = 7.2 Hz, 1H), 3.90 (s, 3H), 2.39 (s, 3H), 1.39 (d, J = 6.4 Hz, 3H), 1.30 (d, J = 7.2 Hz, 3H). ¹³C NMR (151 MHz, CDCl₃) δ 171.83, 168.89, 162.35, 159.47, 157.08, 146.63, 141.44, 137.51, 129.87-129.60 (m), 129.52, 121.60, 121.01-120.03 (m), 115.60, 111.99 (d, J = 21.3 Hz), 109.78, 104.59-102.56 (m), 73.99, 72.93, 56.28, 47.88, 20.74, 18.36, 15.97. ¹⁹F NMR (376 MHz, CDCl₃) δ-109.62 (d, J = 7.6 Hz), −113.92 (d, J = 7.5 Hz). 252 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.28 ([M + H]⁺) calcd for (d, J = 7.8 Hz, 1H), 8.24 (d, J = 5.4 C₂₉H₃₃N₂O₈, Hz, 1H), 7.28 (d, J = 8.0 Hz, 2H), 537.2231; found, 7.19-7.10 (m, 4H), 6.93 (d, J = 5.4 537.2235. Hz, 1H), 6.87 (t, J = 7.4 Hz, 1H), 6.84-6.80 (m, 2H), 5.75-5.70 (m, 2H), 5.26 (dt, J = 11.4, 5.7 Hz, 1H), 5.18 (d, J = 5.0 Hz, 1H), 4.67 (p, J = 7.2 Hz, 1H), 3.90 (s, 3H), 2.31 (s, 3H), 2.06 (s, 3H), 1.38 (d, J = 6.4 Hz, 3H), 1.28 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.25, 170.27, 162.95, 160.27, 157.96, 145.68, 144.01, 142.49, 137.82, 134.51, 129.31, 129.19, 126.89, 121.06, 115.98, 109.53, 89.58, 81.10, 74.38, 56.17, 48.16, 21.14, 20.87, 18.23, 15.00. 253 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.30-8.21 ([M + H]⁺) calcd for (m, 2H), 7.25 (d, J = 7.7 Hz, C₂₉H₃₂FN₂O₈, 2H), 7.12 (d, J = 7.8 Hz, 2H), 6.93 555.2142; found, (d, J = 5.4 Hz, 1H), 6.86-6.80 (m, 555.2138 2H), 6.80-6.66 (m, 2H), 5.77-5.68 (m, 2H), 5.32-5.18 (m, 1H), 5.09 (d, J = 4.8 Hz, 1H), 4.76-4.59 (m, 1H), 3.90 (s, 3H), 2.31 (s, 3H), 2.06 (s, 3H), 1.36 (d, J = 6.4 Hz, 3H), 1.29 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.17, 170.21, 162.97, 160.29, 157.37 (d, J = 238.8 Hz), 154.09 (d, J = 2.1 Hz), 145.64, 144.02, 142.48, 137.97, 134.24, 129.23, 126.87, 117.13 (d, J = 7.9 Hz), 115.66 (d, J = 23.1 Hz), 109.55, 89.56, 82.06, 74.25, 56.15, 48.20, 21.11, 20.83, 18.16, 14.83. ¹⁹F NMR (376 MHz, CDCl₃) δ-123.35. 254 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.30-8.16 ([M + H]⁺) calcd for (m, 2H), 7.41-7.30 (m, 2H), C₂₈H₂₉F₂N₂O₈, 7.01 (t, J = 8.6 Hz, 2H), 6.94 (d, J = 559.1892; found, 5.4 Hz, 1H), 6.89-6.79 (m, 2H), 559.1891 6.81-6.69 (m, 2H), 5.81-5.64 (m, 2H), 5.32-5.18 (m, 1H), 5.10 (d, J = 5.1 Hz, 1H), 4.66 (p, J = 7.3 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.37 (d, J = 6.4 Hz, 3H), 1.30 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-113.53, −122.83. 255 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.30 ([M + H]⁺) calcd for (d, J = 7.8 Hz, 1H), 8.22 (d, J = 5.4 C₂₉H₃₃N₂O₉, Hz, 1H), 7.39 (d, J = 7.6 Hz, 1H), 553.2181; found, 7.26-7.21 (m, 1H), 7.15 (t, J = 8.0 553.2183. Hz, 2H), 6.93-6.80 (m, 6H), 5.75-5.70 (m, 2H), 5.69 (d, J = 4.6 Hz, 1H), 5.43-5.36 (m, 1H), 4.68 (p, J = 7.2 Hz, 1H), 3.90 (d, J = 6.0 Hz, 6H), 2.06 (s, 3H), 1.34 (d, J = 6.5 Hz, 3H), 1.30 (d, J = 7.1 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.11, 170.21, 162.92, 160.25, 157.93, 156.67, 145.64, 143.96, 142.63, 129.26, 129.09, 127.86, 125.54, 120.84, 115.66, 110.20, 109.49, 89.59, 74.92, 73.12, 56.14, 55.47, 48.21, 20.84, 18.27, 15.04. 256 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.29 ([M + H]⁺) calcd for (d, J = 7.7 Hz, 1H), 8.22 (d, J = 5.4 C₂₉H₃₂N₂O₉, Hz, 1H), 7.37-7.31 (m, 1H), 7.16 (t, 571.2086; found, J = 7.9 Hz, 2H), 6.92 (d, J = 5.4 Hz, 571.2095. 1H), 6.86 (t, J = 7.3 Hz, 1H), 6.80 (d, J = 8.1 Hz, 2H), 6.59 (ddd, J = 10.5, 9.5, 2.2 Hz, 2H), 5.75-5.71 (m, 2H), 5.61 (d, J = 4.7 Hz, 1H), 5.40-5.32 (m, 1H), 4.69 (p, J = 7.3 Hz, 1H), 3.90 (s, 6H), 2.06 (s, 3H), 1.35-1.28 (m, 6H). ¹³C NMR (101 MHz, CDCl₃) δ 172.06, 170.21, 163.39 (d, J = 246.1 Hz), 162.93, 160.27, 157.85 (d, J = 9.7 Hz), 157.69, 145.64, 143.99, 142.57, 129.31, 129.04 (d, J = 10.1 Hz), 121.30 (d, J = 3.2 Hz), 121.02, 115.62, 109.52, 107.37 (d, J = 21.2 Hz), 98.67 (d, J = 25.8 Hz), 89.58, 74.54, 72.98, 56.15, 55.78, 48.18, 20.83, 18.26, 15.11. ¹⁹F NMR (376 MHz, CDCl₃) δ-111.31 (s, 1F). 257 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.27 ([M + H]⁺) calcd for (d, J = 7.7 Hz, 1H), 8.24 (d, J = 5.4 C₃₀H₃₅N₂O₈, Hz, 1H), 7.27 (d, J = 7.6 Hz, 2H), 551.2388; found, 7.10 (d, J = 7.7 Hz, 2H), 6.97-6.91 551.2394 (m, 3H), 6.80-6.68 (m, 2H), 5.72 (d, J = 2.5 Hz, 2H), 5.30-5.21 (m, 1H), 5.13 (d, J = 5.1 Hz, 1H), 4.66 (p, J = 7.3 Hz, 1H), 3.89 (s, 3H), 2.30 (s, 3H), 2.20 (s, 3H), 1.37 (d, J = 6.4 Hz, 3H), 1.28 (d, J = 7.3 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.19, 170.16, 162.94, 160.26, 155.85, 145.64, 143.96, 142.55, 137.69, 134.70, 130.26, 129.72, 129.11, 126.90, 115.86, 109.53, 89.52, 81.30, 74.34, 56.13, 48.16, 21.08, 20.80, 20.38, 18.19, 15.01. 258 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.28 ([M + H]⁺) calcd for (d, J = 7.9 Hz, 1H), 8.24 (d, J = 5.4 C₂₉H₃₃N₂O₉, Hz, 1H), 7.23 (t, J = 7.9 Hz, 1H), 553.2181; found, 7.20-7.14 (m, 2H), 6.99 (d, J = 7.7 553.2187. Hz, 1H), 6.95-6.91 (m, 2H), 6.90-6.78 (m, 4H), 5.75-5.70 (m, 2H), 5.26 (dt, J = 11.4, 5.7 Hz, 1H), 5.19 (d, J = 5.0 Hz, 1H), 4.67 (p, J = 7.2 Hz, 1H), 3.90 (s, 3H), 3.76 (d, J = 6.6 Hz, 3H), 2.06 (s, 3H), 1.39 (d, J = 6.4 Hz, 3H), 1.28 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.24, 170.22, 162.97, 160.27, 159.78, 157.98, 145.67, 144.00, 142.50, 139.30, 129.54, 129.33, 121.19, 119.35, 115.99, 113.51, 112.48, 109.54, 89.56, 81.17, 74.33, 56.15, 55.20, 48.16, 20.84, 18.17, 14.96. 259 HRMS-ESI (m/z) ¹H NMR (300 MHz, CDCl₃) δ 8.25 ([M + H]⁺) calcd for (t, J = 7.0 Hz, 2H), 7.38 (dd, J = C₂₉H₃₂FN₂O₈, 8.5, 5.9 Hz, 1H), 7.21-7.13 (m, 555.2137; found, 2H), 6.93 (d, J = 5.4 Hz, 1H), 6.92-6.79 555.2146. (m, 3H), 6.77-6.71 (m, 2H), 5.76-5.68 (m, 2H), 5.39 (d, J = 5.0 Hz, 1H), 5.26-5.15 (m, 1H), 4.66 (p, J = 7.2 Hz, 1H), 3.90 (s, 3H), 2.51 (s, 3H), 2.06 (s, 3H), 1.43 (d, J = 6.4 Hz, 3H), 1.23 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.31, 170.23, 162.98, 162.17 (d, J = 246.4 Hz), 160.29, 157.73, 145.65, 144.04, 142.39, 137.90 (d, J = 7.9 Hz), 131.54 (d, J = 3.0 Hz), 129.41, 128.68 (d, J = 8.5 Hz), 121.29, 117.15 (d, J = 21.2 Hz), 115.75, 113.22 (d, J = 21.2 Hz), 109.57, 89.56, 77.76, 73.35, 56.16, 48.11, 20.84, 19.29 (d, J = 1.1 Hz), 18.03, 14.86. ¹⁹F NMR (376 MHz, CDCl₃) δ-114.90. 260 HRMS-ESI (m/z) ¹H NMR (300 MHz, CDCl₃) δ 8.28 ([M + H]⁺) calcd for (d, J = 7.9 Hz, 1H), 8.24 (d, J = 5.4 C₂₈H₂₉ClFN₂O₈, Hz, 1H), 7.49 (dd, J = 8.8, 6.1 Hz, 575.1591; found, 1H), 7.24-7.15 (m, 2H), 7.14-7.09 575.1596. (m, 1H), 6.97-6.87 (m, 3H), 6.82-6.76 (m, 2H), 5.76-5.70 (m, 2H), 5.63 (d, J = 5.4 Hz, 1H), 5.41-5.31 (m, 1H), 4.70 (p, J = 7.2 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.41 (d, J = 6.4 Hz, 3H), 1.31 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.96, 170.22, 162.94, 162.06 (d, J = 251.0 Hz), 160.29, 157.12, 145.64, 144.03, 142.45, 133.97 (d, J = 10.2 Hz), 131.24 (d, J = 3.5 Hz), 130.03 (d, J = 8.9 Hz), 129.52, 121.51, 116.69 (d, J = 24.7 Hz), 115.56, 114.80 (d, J = 21.2 Hz), 109.57, 89.55, 76.67, 72.95, 56.16, 48.13, 20.84, 18.16, 15.62. ¹⁹F NMR (376 MHz, CDCl₃) δ-111.30. 261 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.29 ([M + H]⁺) calcd for (d, J = 7.8 Hz, 1H), 8.25 (d, J = 5.4 C₂₉H₃₂FN₂O₈, Hz, 1H), 7.31 (t, J = 7.7 Hz, 1H), 555.2137; found, 7.22-7.15 (m, 2H), 6.93 (d, J = 5.4 555.2145. Hz, 1H), 6.87 (ddd, J = 17.3, 7.4, 4.4 Hz, 5H), 5.76-5.70 (m, 2H), 5.50 (d, J = 5.6 Hz, 1H), 5.38 (p, J = 6.2 Hz, 1H), 4.68 (p, J = 7.2 Hz, 1H), 3.90 (s, 3H), 2.30 (s, 3H), 2.06 (s, 3H), 1.40 (d, J = 6.4 Hz, 3H), 1.30 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.01, 170.23, 162.91, 160.27, 160.25 (d, J = 245.8 Hz), 157.41, 145.65, 143.99, 142.56, 140.44 (d, J = 8.0 Hz), 129.41, 128.26 (d, J = 4.2 Hz), 125.32 (d, J = 3.0 Hz), 121.39 (d, J = 13.3 Hz), 121.29, 115.67 (d, J = 21.6 Hz), 115.61, 109.52, 89.57, 74.35, 73.10, 56.15, 48.14, 21.05 (d, J = 1.3 Hz), 20.84, 18.20, 15.84. ¹⁹F NMR (376 MHz, CDCl₃) δ-119.14. 262 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.43 ([M + H]⁺) calcd for (d, J = 8.5 Hz, 1H), 8.27 (d, J = 7.9 C₃₂H₃₃N₂O₈, Hz, 1H), 8.25 (d, J = 5.4 Hz, 1H), 573.2231; found, 7.89 (d, J = 8.0 Hz, 1H), 7.79 (d, J = 573.2238. 8.2 Hz, 1H), 7.63 (dd, J = 11.1, 4.1 Hz, 2H), 7.53 (t, J = 7.1 Hz, 1H), 7.45-7.38 (m, 1H), 7.15-7.08 (m, 2H), 6.93 (d, J = 5.4 Hz, 1H), 6.84 (t, J = 7.4 Hz, 1H), 6.82-6.77 (m, 2H), 6.12 (d, J = 4.1 Hz, 1H), 5.75-5.69 (m, 2H), 5.49-5.41 (m, 1H), 4.67 (p, J = 7.2 Hz, 1H), 3.90 (s, 3H), 2.06 (s, 3H), 1.42 (d, J = 6.5 Hz, 3H), 1.14 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.73, 170.24, 163.00, 160.30, 158.04, 145.66, 144.05, 142.46, 133.73, 133.05, 130.59, 129.36, 128.98, 128.64, 126.82, 125.84, 125.46, 124.71, 122.94, 121.09, 115.69, 109.56, 89.59, 77.50, 73.92, 56.16, 48.11, 20.85, 17.93, 14.33. 263 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.26 ([M + H]⁺) calcd for (d, J = 7.8 Hz, 1H), 8.23 (d, J = 5.4 C₃₂H₃₃N₂O₈, Hz, 1H), 7.86 (s, 1H), 7.80 (dd, J = 573.2231; found, 8.5, 6.2 Hz, 3H), 7.54 (dd, J = 8.5, 573.2236. 1.6 Hz, 1H), 7.49-7.44 (m, 2H), 7.18-7.12 (m, 2H), 6.92 (d, J = 5.4 Hz, 1H), 6.86 (dd, J = 10.9, 4.3 Hz, 3H), 5.74-5.69 (m, 2H), 5.42-5.34 (m, 2H), 4.67 (p, J = 7.2 Hz, 1H), 3.90 (s, 3H), 2.05 (s, 3H), 1.43 (d, J = 6.2 Hz, 3H), 1.23 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.27, 170.22, 162.96, 160.27, 157.99, 145.66, 144.01, 142.48, 135.18, 133.17, 133.10, 129.36, 128.44, 127.94, 127.72, 126.29, 126.17, 124.38, 121.24, 116.08, 109.54, 89.57, 81.46, 74.38, 56.16, 48.15, 20.85, 18.16, 14.98. 264 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.50 ([M + H]⁺) calcd for (d, J = 5.5 Hz, 1H), 8.27 (d, J = 5.4 C₃₀H₃₂FN₂O₈, Hz, 1H), 7.35 (t, J = 7.6 Hz, 1H), 567.2137; found, 7.19-7.13 (m, 2H), 6.98 (d, J = 5.5 567.2148. Hz, 1H), 6.87 (t, J = 7.3 Hz, 1H), 6.84-6.78 (m, 2H), 6.63-6.55 (m, 2H), 6.09 (ddt, J = 17.2, 10.4, 5.1 Hz, 1H), 5.65 (d, J = 4.6 Hz, 1H), 5.47 (ddd, J = 17.3, 3.0, 1.5 Hz, 1H), 5.42-5.32 (m, 2H), 4.72-4.63 (m, 1H), 4.61 (d, J = 5.0 Hz, 2H), 3.90 (s, 3H), 2.39 (s, 3H), 1.35-1.29 (m, 6H). ¹³C NMR (101 MHz, CDCl₃) δ 171.94, 168.86, 163.21 (d, J = 246.3 Hz), 162.34, 159.44, 157.65, 156.74 (d, J = 10.0 Hz), 146.62, 141.58, 137.49, 132.40, 129.31, 129.21 (d, J = 10.2 Hz), 121.48 (d, J = 3.2 Hz), 121.03, 117.97, 115.64, 109.71, 107.60 (d, J = 21.4 Hz), 99.80 (d, J = 25.8 Hz), 74.56, 73.01, 69.22, 56.26, 47.97, 20.73, 18.50, 15.24. ¹⁹F NMR (376 MHz, CDCl₃) δ-111.31. 265 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.50 ([M + H]⁺) calcd for (d, J = 5.8 Hz, 1H), 8.28 (d, J = 5.1 C₂₉H₃₂FN₂O₈, Hz, 1H), 7.33 (dd, J = 8.3, 6.9 Hz, 555.2137; found, 1H), 7.17 (dd, J = 8.5, 7.5 Hz, 2H), 555.2143. 6.98 (d, J = 5.4 Hz, 1H), 6.87 (t, J = 7.3 Hz, 1H), 6.81 (d, J = 7.9 Hz, 2H), 6.62-6.53 (m, 2H), 5.61 (d, J = 4.5 Hz, 1H), 5.43-5.35 (m, 1H), 4.68 (p, J = 7.2 Hz, 1H), 4.09 (tt, J = 8.1, 4.1 Hz, 2H), 3.90 (s, 3H), 2.39 (s, 3H), 1.49 (t, J = 7.0 Hz, 3H), 1.32 (d, J = 6.8 Hz, 6H). ¹⁹F NMR (376 MHz, CDCl₃) δ-111.56. 266 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.50 ([M + H]⁺) calcd for (d, J = 6.6 Hz, 1H), 8.28 (d, J = 5.4 C₂₉H₃₁ClFN₂O₈, Hz, 1H), 7.38 (dd, J = 9.2, 6.7 Hz, 589.1747; found, 1H), 7.12 (d, J = 1.7 Hz, 1H), 6.98 589.1749. (d, J = 5.5 Hz, 1H), 6.81-6.76 (m, 1H), 6.61 (ddd, J = 10.8, 5.5, 2.3 Hz, 2H), 6.55 (d, J = 8.4 Hz, 1H), 5.63 (d, J = 4.4 Hz, 1H), 5.42-5.35 (m, 1H), 4.72-4.64 (m, 1H), 3.90 (s, 3H), 3.88 (s, 3H), 2.39 (s, 3H), 2.19 (s, 3H), 1.35 (d, J = 6.5 Hz, 3H), 1.33 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.95, 168.85, 163.47 (d, J = 246.5 Hz), 159.42, 162.34, 157.82 (d, J = 9.7 Hz), 150.89, 146.60, 141.58, 137.48, 131.22, 130.67, 129.17 (d, J = 10.1 Hz), 127.84, 122.93, 120.74 (d, J = 3.4 Hz), 114.38, 109.67, 107.46 (d, J = 21.3 Hz), 98.64 (d, J = 25.9 Hz), 75.32, 73.02, 56.25, 55.78, 47.97, 20.71, 20.20, 18.44, 14.99. ¹⁹F NMR (376 MHz, CDCl₃) δ-110.97 (d, J = 2.0 Hz). 267 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.41 ([M + H]⁺) calcd for (d, J = 6.8 Hz, 1H), 8.29 (d, J = 5.4 C₂₉H₃₀FN₂O₉, Hz, 1H), 7.41 (dd, J = 9.4, 6.2 Hz, 569.1930; found, 1H), 7.17 (dd, J = 8.5, 7.5 Hz, 2H), 569.1951. 6.98 (d, J = 5.5 Hz, 1H), 6.90 (tt, J = 7.5, 3.9 Hz, 3H), 6.78 (d, J = 8.0 Hz, 2H), 5.43 (d, J = 3.9 Hz, 1H), 5.23 (qd, J = 6.5, 4.0 Hz, 1H), 4.65 (p, J = 7.2 Hz, 1H), 3.90 (s, 3H), 2.44 (s, 3H), 2.38 (s, 3H), 1.32 (d, J = 6.6 Hz, 3H), 1.28 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.13, 169.16, 168.84, 162.39, 162.31 (d, J = 248.8 Hz), 159.45, 157.63, 148.71 (d, J = 10.9 Hz), 146.58, 141.52, 137.52, 129.46, 129.05 (d, J = 9.4 Hz), 125.46 (d, J = 3.6 Hz), 121.41, 115.63, 113.49 (d, J = 21.2 Hz), 110.65 (d, J = 24.6 Hz), 109.74, 75.35, 72.75, 56.26, 47.94, 21.01, 20.72, 18.26, 13.95. ¹⁹F NMR (376 MHz, CDCl₃) δ −111.42. 268 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.50 ([M + H]⁺) calcd for (d, J = 6.4 Hz, 1H), 8.28 (d, J = 5.4 C₃₀H₃₄FN₂O₈, Hz, 1H), 7.33 (dd, J = 8.3, 6.8 Hz, 569.2294; found, 1H), 7.20-7.13 (m, 2H), 6.98 (d, J = 569.2289. 5.5 Hz, 1H), 6.87 (t, J = 7.3 Hz, 1H), 6.83-6.79 (m, 2H), 6.62-6.53 (m, 2H), 5.62 (d, J = 4.6 Hz, 1H), 5.41-5.33 (m, 1H), 4.67 (p, J = 7.2 Hz, 1H), 3.98 (t, J = 6.4 Hz, 2H), 3.90 (s, 3H), 2.39 (s, 3H), 1.95-1.85 (m, 2H), 1.32 (t, J = 7.0 Hz, 6H), 1.10 (t, J = 7.4 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.95, 168.86, 163.31 (d, J = 246.0 Hz), 162.33, 159.43, 157.73, 157.24 (d, J = 9.8 Hz), 146.62, 141.59, 137.48, 129.30, 129.00 (d, J = 10.2 Hz), 121.22 (d, J = 3.2 Hz), 120.97, 115.59, 109.69, 107.15 (d, J = 21.3 Hz), 99.21 (d, J = 25.7 Hz), 74.62, 73.06, 69.99, 56.25, 47.96, 22.49, 20.72, 18.51, 15.18, 10.68. ¹⁹F NMR (376 MHz, CDCl₃) δ-111.49. 269 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.52 ([M + H]⁺) calcd for (d, J = 5.5 Hz, 1H), 8.26 (d, J = 5.4 C₂₉H₃₃N₂O₈, Hz, 1H), 7.24 (s, 1H), 7.18-7.12 537.2231; found, (m, 2H), 6.97 (d, J = 5.5 Hz, 1H), 537.2220. 6.84 (dd, J = 14.9, 7.6 Hz, 3H), 6.70 (d, J = 6.4 Hz, 2H), 5.63 (d, J = 4.5 Hz, 1H), 5.40-5.33 (m, 1H), 4.67 (p, J = 7.2 Hz, 1H), 3.89 (s, 3H), 3.89 (s, 3H), 2.39 (s, 3H), 2.31 (s, 3H), 1.32 (d, J = 6.5 Hz, 3H), 1.30 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.02, 168.85, 162.32, 159.41, 157.97, 156.57, 146.60, 141.65, 139.16, 137.46, 129.23, 127.70, 122.40, 121.51, 120.73, 115.65, 111.09, 109.64, 74.86, 73.22, 56.24, 55.40, 48.01, 21.56, 20.73, 18.47, 14.97. 270 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.50 ([M + H]⁺) calcd for (d, J = 5.6 Hz, 1H), 8.26 (d, J = 5.4 C₂₈H₃₀FN₂O₈, Hz, 1H), 7.34 (dd, J = 8.4, 6.8 Hz, 541.1981; found, 1H), 7.20-7.13 (m, 2H), 6.97 (d, J = 541.1987. 5.5 Hz, 1H), 6.87 (t, J = 7.3 Hz, 1H), 6.83-6.78 (m, 2H), 6.63-6.55 (m, 2H), 5.61 (d, J = 4.7 Hz, 1H), 5.39-5.31 (m, 1H), 4.68 (p, J = 7.2 Hz, 1H), 3.89 (s, 6H), 2.39 (s, 3H), 1.34-1.28 (m, 6H). ¹³C NMR (101 MHz, CDCl₃) δ 171.95, 168.85, 163.38 (d, J = 246.3 Hz), 162.34, 159.44, 157.84 (d, J = 9.8 Hz), 157.69, 146.61, 141.57, 137.49, 129.31, 129.05 (d, J = 10.1 Hz), 121.27 (d, J = 3.3 Hz), 121.02, 115.63, 109.70, 107.36 (d, J = 21.4 Hz), 98.66 (d, J = 25.8 Hz), 74.52, 73.01, 56.25, 55.77, 47.97, 20.72, 18.45, 15.10. ¹⁹F NMR (376 MHz, CDCl₃) δ-111.28. 271 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.50 ([M + H]⁺) calcd for (d, J = 5.4 Hz, 1H), 8.27 (d, J = 5.4 C₂₉H₃₂FN₂O₈, Hz, 1H), 7.36-7.31 (m, 1H), 7.00-6.93 555.2137; found, (m, 3H), 6.70 (t, J = 5.7 Hz, 555.2136. 2H), 6.62-6.55 (m, 2H), 5.56 (d, J = 4.7 Hz, 1H), 5.37-5.30 (m, 1H), 4.67 (p, J = 7.2 Hz, 1H), 3.90 (s, 3H), 3.88 (s, 3H), 2.39 (s, 3H), 2.21 (s, 3H), 1.33-1.28 (m, 6H). ¹³C NMR (101 MHz, CDCl₃) δ 171.97, 168.85, 163.34 (d, J = 246.0 Hz), 162.33, 159.44, 157.85 (d, J = 9.7 Hz), 155.58, 146.61, 141.59, 137.49, 130.22, 129.76, 129.07 (d, J = 10.1 Hz), 121.46 (d, J = 3.0 Hz), 115.48, 109.68, 107.33 (d, J = 21.4 Hz), 98.63 (d, J = 25.9 Hz), 74.66, 73.04, 56.25, 55.75, 47.96, 20.72, 20.42, 18.46, 15.11. ¹⁹F NMR (376 MHz, CDCl₃) δ-111.44. 272 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.50 ([M + H]⁺) calcd for (d, J = 5.6 Hz, 1H), 8.28 (d, J = 5.4 C₃₁H₃₄FN₂O₈, Hz, 1H), 7.34 (dd, J = 9.2, 6.7 Hz, 581.2294; found, 1H), 7.17 (dd, J = 8.5, 7.5 Hz, 2H), 581.2296. 6.98 (d, J = 5.5 Hz, 1H), 6.90-6.81 (m, 3H), 6.59-6.53 (m, 2H), 5.66 (d, J = 4.6 Hz, 1H), 5.44-5.37 (m, 1H), 4.68 (p, J = 7.1 Hz, 1H), 3.90 (s, 3H), 3.88 (d, J = 7.0 Hz, 2H), 2.39 (s, 3H), 1.36-1.26 (m, 7H), 0.71-0.64 (m, 2H), 0.40 (q, J = 4.7 Hz, 2H). ¹³C NMR (101 MHz, CDCl₃) δ 171.93, 168.85, 163.27 (d, J = 246.3 Hz), 162.33, 159.44, 157.71, 157.13 (d, J = 9.9 Hz), 146.62, 141.60, 137.49, 129.29, 129.13 (d, J = 10.2 Hz), 121.35 (d, J = 3.1 Hz), 120.95, 115.61, 109.69, 107.23 (d, J = 21.3 Hz), 99.37 (d, J = 25.8 Hz), 74.52, 73.11, 72.95, 56.25, 47.98, 20.72, 18.55, 15.31, 10.08, 3.26, 3.12. ¹⁹F NMR (376 MHz, CDCl₃) δ-111.49. 273 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.46 ([M + H]⁺) calcd for (d, J = 7.3 Hz, 1H), 8.29 (d, J = 5.4 C₂₉H₃₀F₃N₂O₈, Hz, 1H), 7.38 (dd, J = 8.6, 6.6 Hz, 591.1949; found, 1H), 7.21-7.14 (m, 2H), 6.99 (d, J = 591.1943. 5.5 Hz, 1H), 6.88 (t, J = 7.4 Hz, 1H), 6.82-6.77 (m, 2H), 6.67 (td, J = 8.3, 2.3 Hz, 1H), 6.59 (dd, J = 10.2, 2.3 Hz, 1H), 6.23 (tt, J = 54.8, 4.0 Hz, 1H), 5.60 (d, J = 4.3 Hz, 1H), 5.40-5.32 (m, 1H), 4.66 (p, J = 7.2 Hz, 1H), 4.31-4.17 (m, 2H), 3.90 (s, 3H), 2.39 (s, 3H), 1.33 (d, J = 3.8 Hz, 3H), 1.31 (d, J = 4.4 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.96, 168.87, 163.12 (d, J = 247.7 Hz), 162.36, 159.46, 157.56, 155.60 (d, J = 9.7 Hz), 146.63, 141.54, 137.51, 129.58 (d, J = 9.9 Hz), 129.39, 121.84 (d, J = 3.5 Hz), 121.23, 115.62, 109.74, 108.83 (d, J = 21.1 Hz), 99.64 (d, J = 26.1 Hz), 74.60, 72.81, 68.12-66.92 (m), 56.27, 47.93, 20.71, 18.42, 14.85. ¹⁹F NMR (376 MHz, CDCl₃) δ-110.59, −124.95 (d, J = 296.7 Hz), −125.92 (d, J = 296.7 Hz). 274 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.52 ([M + H]⁺) calcd for (d, J = 4.2 Hz, 1H), 8.27 (d, J = 5.4 C₃₀H₃₅N₂O₈, Hz, 1H), 7.24 (d, J = 7.7 Hz, 1H), 551.2388; found, 6.96 (dd, J = 10.9, 7.0 Hz, 3H), 6.75-6.66 551.2384. (m, 4H), 5.58 (d, J = 4.5 Hz, 1H), 5.41-5.31 (m, 1H), 4.67 (p, J = 7.2 Hz, 1H), 3.90 (s, 3H), 3.87 (s, 3H), 2.39 (s, 3H), 2.30 (s, 3H), 2.20 (s, 3H), 1.34-1.27 (m, 6H). ¹³C NMR (101 MHz, CDCl₃) δ 172.04, 168.87, 162.32, 159.42, 156.59, 155.86, 146.60, 141.66, 139.07, 137.47, 129.89, 129.69, 127.72, 122.60, 121.50, 115.50, 111.07, 109.64, 74.99, 73.26, 56.24, 55.38, 48.02, 21.56, 20.72, 20.41, 18.48, 14.97. 275 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.49 ([M + H]⁺) calcd for (d, J = 6.7 Hz, 1H), 8.27 (d, J = 5.4 C₃₁H₃₄FN₂O₈, Hz, 1H), 7.48 (dd, J = 8.7, 6.5 Hz, 603.2137; found, 1H), 7.44-7.38 (m, 2H), 7.24-7.15 603.2133. (m, 3H), 7.12-7.06 (m, 2H), 6.98 (d, J = 5.5 Hz, 1H), 6.93-6.84 (m, 3H), 6.71 (td, J = 8.3, 2.5 Hz, 1H), 6.48 (dd, J = 10.1, 2.5 Hz, 1H), 5.72 (d, J = 5.0 Hz, 1H), 5.52-5.44 (m, 1H), 4.71 (p, J = 7.2 Hz, 1H), 3.89 (s, 3H), 2.39 (s, 3H), 1.40 (d, J = 6.4 Hz, 3H), 1.34 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-110.73. 276 ESIMS m/z 336 ([M + H]⁺) 277 ESIMS m/z 254 ([M − OCH₂cPr]⁺) 278 ESIMS m/z 356 ([M + H]⁺) 279 ESIMS m/z 340 ([M + H]⁺) 280 ESIMS m/z 312 ([M + H]⁺) 281 ESIMS m/z 312 ([M + H]⁺) 282 ESIMS m/z 458 ¹H NMR (400 MHz, CDCl₃) δ 7.31 ([M + Na]⁺) (dd, J = 8.5, 6.7 Hz, 1H), 6.69 (td, J = 8.3, 2.4 Hz, 1H), 6.60 (dd, J = 10.8, 2.4 Hz, 1H), 5.85 (tt, J = 55.4, 4.1 Hz, 1H), 5.22-5.12 (m, 1H), 5.01 (d, J = 8.2 Hz, 1H), 4.84 (d, J = 5.0 Hz, 1H), 4.25 (t, J = 7.5 Hz, 1H), 3.82 (s, 3H), 3.64-3.50 (m, 2H), 1.44 (s, 9H), 1.24-1.17 (m, 6H). ¹⁹F NMR (471 MHz, CDCl₃) δ-111.01(dd, J = 16.7, 7.9 Hz), −124.47-125.21 (m), −125.21-125.96 (m). 283 ESIMS m/z 448 ¹H NMR (400 MHz, CDCl₃) δ 7.34 ([M + Na]⁺) (dd, J = 8.3, 7.0 Hz, 1H), 6.66 (td, J = 8.3, 2.3 Hz, 1H), 6.57 (dd, J = 10.9, 2.3 Hz, 1H), 5.14 (p, J = 6.3 Hz, 1H), 5.04 (d, J = 6.4 Hz, 1H), 4.78 (d, J = 5.5 Hz, 1H), 4.29-4.17 (m, 1H), 3.81 (s, 3H), 3.18 (qd, J = 10.3, 6.8 Hz, 2H), 1.43 (s, 9H), 1.24 (d, J = 6.4 Hz, 3H), 1.18 (d, J = 7.2 Hz, 3H), 1.06-0.95 (m, 1H), 0.54-0.41 (m, 2H), 0.12 (dqd, J = 14.0, 9.3, 4.7 Hz, 2H). ¹⁹F NMR (376 MHz, CDCl₃) δ-112.12 (s). 284 ESIMS m/z 478 ¹H NMR (400 MHz, CDCl₃) δ 7.26-7.21 ([M + Na]⁺) (m, 1H), 6.65 (td, J = 8.3, 2.4 Hz, 1H), 6.60 (dd, J = 10.8, 2.4 Hz, 1H), 6.23 (d, J = 4.2 Hz, 1H), 5.36-5.28 (m, 1H), 5.05 (d, J = 7.4 Hz, 1H), 4.33-4.20 (m, 1H), 3.84 (s, 3H), 1.44 (s, 9H), 1.29 (d, J = 7.2 Hz, 3H), 1.24 (s, 9H), 1.19 (d, J = 6.5 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ-111.22 (s). 285 ESIMS m/z 462 ¹H NMR (300 MHz, CDCl₃) δ 7.31-7.27 ([M + Na]⁺) (m, 1H), 6.66 (td, J = 8.3, 2.4 Hz, 1H), 6.59 (dd, J = 10.8, 2.4 Hz, 1H), 6.26 (d, J = 4.2 Hz, 1H), 5.37-5.27 (m, 1H), 5.04 (d, J = 7.7 Hz, 1H), 4.35-4.21 (m, 1H), 3.83 (s, 3H), 1.68 (ddd, J = 15.2, 7.9, 4.6 Hz, 1H), 1.44 (s, 9H), 1.28 (d, J = 7.2 Hz, 3H), 1.18 (d, J = 6.5 Hz, 3H), 1.08-0.84 (m, 4H). 286 ESIMS m/z 434 ¹H NMR (400 MHz, CDCl₃) δ 7.41-7.35 ([M + Na]⁺) (m, 1H), 6.67 (td, J = 8.3, 2.4 Hz, 1H), 6.60 (dd, J = 10.9, 2.4 Hz, 1H), 5.20-5.12 (m, 1H), 5.02 (d, J = 6.6 Hz, 1H), 4.79 (d, J = 5.7 Hz, 1H), 4.31-4.19 (m, 1H), 3.83 (s, 3H), 3.19 (ddd, J = 8.8, 6.1, 3.0 Hz, 1H), 1.43 (s, 9H), 1.27-1.19 (m, 3H), 1.14 (dd, J = 12.7, 6.1 Hz, 3H), 0.69-0.62 (m, 1H), 0.56-0.42 (m, 2H), 0.36 (dt, J = 13.0, 5.6 Hz, 1H). ¹⁹F NMR (376 MHz, CDCl₃) δ-111.92 (s). 287 ESIMS m/z 434 ¹H NMR (400 MHz, CDCl₃) δ 7.36 ([M + Na]⁺) (dd, J = 8.3, 7.0 Hz, 1H), 6.67 (td, J = 8.4, 2.3 Hz, 1H), 6.59 (dd, J = 10.9, 2.3 Hz, 1H), 5.13 (dt, J = 12.8, 6.4 Hz, 1H), 5.03 (d, J = 5.6 Hz, 1H), 4.84 (d, J = 5.0 Hz, 1H), 4.30-4.19 (m, 1H), 3.83 (s, 3H), 3.24 (ddd, J = 8.9, 6.0, 2.8 Hz, 1H), 1.44 (s, 9H), 1.21 (d, J = 7.2 Hz, 3H), 1.16 (d, J = 6.4 Hz, 3H), 0.67-0.60 (m, 1H), 0.57-0.50 (m, 1H), 0.47-0.34 (m, 2H). ¹⁹F NMR (376 MHz, CDCl₃) δ-112.09 (s). 288 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 12.12 ([M + H]⁺) calcd for (s, 1H), 8.43 (d, J = 7.9 Hz, 1H), C₂₂H₂₆F₃N₂O₇, 7.99 (d, J = 5.2 Hz, 1H), 7.31 (dd, J = 487.1687; found, 8.5, 6.8 Hz, 1H), 6.87 (d, J = 5.2 487.1690. Hz, 1H), 6.66 (td, J = 8.3, 2.4 Hz, 1H), 6.59 (dd, J = 10.8, 2.4 Hz, 1H), 5.83 (tt, J = 55.5, 4.1 Hz, 1H), 5.26-5.20 (m, 1H), 4.86 (d, J = 4.8 Hz, 1H), 4.67 (p, J = 7.2 Hz, 1H), 3.94 (s, 3H), 3.81 (s, 3H), 3.62-3.50 (m, 2H), 1.40 (d, J = 7.2 Hz, 3H), 1.24 (d, J = 6.5 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.24, 168.67, 163.50 (d, J = 246.6 Hz), 158.42 (d, J = 9.7 Hz), 155.40, 148.76, 140.49, 130.41, 128.90 (d, J = 10.1 Hz), 120.72 (d, J = 3.2 Hz), 114.27 (t, J = 241.2 Hz), 109.48, 107.23 (d, J = 21.3 Hz), 98.76 (d, J = 25.8 Hz), 77.76, 73.01, 68.71 (t, J = 28.1 Hz), 56.09, 55.68, 48.00, 18.04, 14.82. ¹⁹F NMR (471 MHz, CDCl₃) δ-110.96 (dt, J = 10.7, 7.5 Hz), −124.47-125.22 (m), −125.22-125.96 (m). 289 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 12.15 ([M + H]⁺) calcd for (s, 1H), 8.45 (d, J = 7.8 Hz, 1H), C₂₄H₃₀FN₂O₇, 7.98 (d, J = 5.2 Hz, 1H), 7.34 (dd, J = 477.2032; found, 8.4, 6.9 Hz, 1H), 6.87 (d, J = 5.2 477.2028. Hz, 1H), 6.64 (td, J = 8.3, 2.4 Hz, 1H), 6.56 (dd, J = 10.9, 2.4 Hz, 1H), 5.24-5.18 (m, 1H), 4.80 (d, J = 5.3 Hz, 1H), 4.65 (p, J = 7.2 Hz, 1H), 3.94 (s, 3H), 3.80 (s, 3H), 3.21 (dd, J = 10.3, 6.7 Hz, 1H), 3.15 (dd, J = 10.2, 6.9 Hz, 1H), 1.36 (d, J = 7.2 Hz, 3H), 1.26 (d, J = 6.4 Hz, 3H), 1.03-0.95 (m, 1H), 0.51-0.40 (m, 2H), 0.16-0.05 (m, 2H). ¹³C NMR (126 MHz, CDCl₃) δ 171.35, 168.62, 163.17 (d, J = 245.6 Hz), 158.46 (d, J = 9.7 Hz), 155.36, 148.73, 140.44, 130.50, 129.05 (d, J = 10.0 Hz), 122.41 (d, J = 3.2 Hz), 109.41, 106.95 (d, J = 21.1 Hz), 98.51 (d, J = 25.7 Hz), 75.99, 73.94, 73.55, 56.07, 55.61, 47.98, 18.09, 15.34, 10.63, 3.12, 2.72. ¹⁹F NMR (471 MHz, CDCl₃) δ-112.03 (dt, J = 10.8, 7.6 Hz). 290 HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 12.13 ([M + H]⁺) calcd for (s, 1H), 8.44 (d, J = 7.9 Hz, 1H), C₂₅H₃₂FN₂O₈, 7.99 (d, J = 5.2 Hz, 1H), 7.24 (dd, J = 507.2137; found, 8.7, 6.6 Hz, 1H), 6.88 (d, J = 5.2 507.2130. Hz, 1H), 6.62-6.55 (m, 2H), 6.25 (d, J = 4.1 Hz, 1H), 5.37 (qd, J = 6.5, 4.2 Hz, 1H), 4.68 (p, J = 7.2 Hz, 1H), 3.95 (s, 3H), 3.84 (s, 3H), 1.46 (d, J = 7.2 Hz, 3H), 1.23 (s, 9H), 1.21 (d, J = 6.6 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 176.88, 171.22, 168.67, 163.44 (d, J = 246.4 Hz), 157.80 (d, J = 9.9 Hz), 155.39, 148.77, 140.48, 130.43, 128.41 (d, J = 10.1 Hz), 120.70 (d, J = 3.3 Hz), 109.48, 106.95 (d, J = 21.4 Hz), 98.89 (d, J = 25.8 Hz), 72.17, 70.06, 56.09, 55.79, 47.93, 38.91, 27.11, 18.17, 14.83. 291 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.13 ([M + H]⁺) calcd for (s, 1H), 8.44 (d, J = 7.8 Hz, 1H), C₂₄H₂₈FN₂O₈, 8.00 (d, J = 5.2 Hz, 1H), 7.30-7.24 491.1824; found, (m, 1H), 6.88 (d, J = 5.2 Hz, 1H), 491.1820 6.59 (t, J = 8.0 Hz, 2H), 6.28 (d, J = 4.2 Hz, 1H), 5.42-5.34 (m, 1H), 4.69 (p, J = 7.3 Hz, 1H), 3.95 (s, 3H), 3.83 (s, 3H), 1.68 (ddd, J = 12.7, 8.2, 4.7 Hz, 1H), 1.46 (d, J = 7.2 Hz, 3H), 1.20 (d, J = 6.5 Hz, 3H), 1.06-0.95 (m, 2H), 0.95-0.83 (m, 2H). ¹³C NMR (101 MHz, CDCl₃) δ 173.42, 171.27, 168.70, 163.47 (d, J = 246.5 Hz), 157.82 (d, J = 9.9 Hz), 155.41, 148.80, 140.46, 130.49, 128.77 (d, J = 10.1 Hz), 120.61 (d, J = 3.3 Hz), 109.49, 106.96 (d, J = 21.4 Hz), 98.88 (d, J = 25.8 Hz), 72.02, 70.17, 56.07, 55.79, 47.97, 18.11, 14.91, 12.97, 8.58. ¹⁹F NMR (376 MHz, CDCl₃) δ-111.11 (s). 292 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 12.15 ([M + H]⁺) calcd for (s, 1H), 8.43 (d, J = 7.7 Hz, 1H), C₂₃H₂₈FN₂O₇, 7.98 (d, J = 5.2 Hz, 1H), 7.39 (dd, J = 463.1875; found, 8.3, 7.0 Hz, 1H), 6.86 (d, J = 5.2 463.1873 Hz, 1H), 6.66-6.57 (m, 2H), 5.24-5.15 (m, 1H), 4.82 (d, J = 5.6 Hz, 1H), 4.70-4.61 (m, 1H), 3.94 (s, 3H), 3.83 (s, 3H), 3.20 (ddd, J = 9.1, 6.1, 3.0 Hz, 1H), 1.39 (d, J = 7.2 Hz, 3H), 1.18 (d, J = 6.5 Hz, 3H), 0.70-0.63 (m, 1H), 0.56-0.42 (m, 2H), 0.39-0.32 (m, 1H). ¹³C NMR (101 MHz, CDCl₃) δ 171.59, 168.55, 163.26 (d, J = 245.8 Hz), 158.24 (d, J = 9.6 Hz), 155.35, 148.75, 140.38, 130.58, 129.23 (d, J = 10.0 Hz), 122.42 (d, J = 3.2 Hz), 109.40, 106.86 (d, J = 21.1 Hz), 98.86 (d, J = 25.7 Hz), 77.62, 73.37, 56.04, 55.67, 52.37, 47.96, 18.40, 16.14, 6.27, 5.48. ¹⁹F NMR (376 MHz, CDCl₃) δ-111.84 (s). 293 ESIMS m/z 485 ¹H NMR (400 MHz, CDCl₃) δ 12.15 ([M + Na]⁺) (s, 1H), 8.45 (d, J = 7.9 Hz, 1H), 7.99 (d, J = 5.1 Hz, 1H), 7.36 (dd, J = 8.3, 7.0 Hz, 1H), 6.87 (d, J = 5.2 Hz, 1H), 6.65 (td, J = 8.4, 2.4 Hz, 1H), 6.59 (dd, J = 10.9, 2.3 Hz, 1H), 5.23-5.15 (m, 1H), 4.86 (d, J = 4.8 Hz, 1H), 4.67 (p, J = 7.3 Hz, 1H), 3.94 (s, 3H), 3.83 (s, 3H), 3.24 (dq, J = 9.0, 3.0 Hz, 1H), 1.40 (d, J = 7.2 Hz, 3H), 1.18 (d, J = 6.4 Hz, 3H), 0.66-0.58 (m, 1H), 0.56-0.49 (m, 1H), 0.46-0.31 (m, 2H). ¹³C NMR (101 MHz, CDCl₃) δ 171.26, 168.61, 163.26 (d, J = 245.7 Hz), 158.24 (d, J = 9.7 Hz), 155.39, 148.78, 140.40, 130.54, 129.24 (d, J = 10.1 Hz), 122.32 (d, J = 3.3 Hz), 109.44, 106.91 (d, J = 21.2 Hz), 98.67 (d, J = 25.7 Hz), 73.08, 56.06, 55.66, 52.43, 48.00, 18.19, 14.83, 6.10, 5.70. ¹⁹F NMR (376 MHz, CDCl₃) δ-112.01 (s). 294 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.48 ([M + H]⁺) calcd for (d, J = 6.8 Hz, 1H), 8.32 (d, J = 5.4 C₂₄H₂₈F₃N₂O₈, Hz, 1H), 7.32 (dd, J = 8.5, 6.8 Hz, 529.1792; found, 1H), 7.00 (d, J = 5.5 Hz, 1H), 6.66 529.1788. (td, J = 8.3, 2.4 Hz, 1H), 6.59 (dd, J = 10.8, 2.4 Hz, 1H), 5.83 (tt, J = 55.5, 4.2 Hz, 1H), 5.24-5.16 (m, 1H), 4.85 (d, J = 4.7 Hz, 1H), 4.67 (p, J = 7.2 Hz, 1H), 3.91 (s, 3H), 3.81 (s, 3H), 3.57 (td, J = 13.8, 4.2 Hz, 2H), 2.39 (s, 3H), 1.34 (d, J = 7.2 Hz, 3H), 1.21 (d, J = 6.5 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.74, 168.86, 163.48 (d, J = 246.5 Hz), 162.35, 159.49, 158.38 (d, J = 9.8 Hz), 146.63, 141.53, 137.54, 128.91 (d, J = 10.0 Hz), 120.94 (d, J = 3.0 Hz), 114.30 (t, J = 241.1 Hz), 109.77, 107.18 (d, J = 21.3 Hz), 98.73 (d, J = 25.8 Hz), 77.81, 72.84, 68.83 (t, J = 28.1 Hz), 56.28, 55.65, 47.99, 20.71, 18.34, 14.74. ¹⁹F NMR (376 MHz, CDCl₃) δ-111.16 (s), −124.83 (d, J = 293.2 Hz), −125.66 (d, J = 293.2 Hz). 295 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.50 ([M + H]⁺) calcd for (d, J = 6.2 Hz, 1H), 8.32 (d, J = 5.4 C₂₆H₃₂FN₂O₈, Hz, 1H), 7.35 (dd, J = 8.3, 7.1 Hz, 519.2137; found, 1H), 6.99 (d, J = 5.5 Hz, 1H), 6.64 519.2131. (td, J = 8.3, 2.3 Hz, 1H), 6.57 (dd, J = 10.9, 2.3 Hz, 1H), 5.18 (p, J = 6.3 Hz, 1H), 4.79 (d, J = 5.4 Hz, 1H), 4.65 (p, J = 7.2 Hz, 1H), 3.90 (s, 3H), 3.80 (s, 3H), 3.22 (dd, J = 10.2, 6.7 Hz, 1H), 3.15 (dd, J = 10.2, 6.9 Hz, 1H), 2.39 (s, 3H), 1.28 (d, J = 7.2 Hz, 3H), 1.25 (d, J = 6.4 Hz, 3H), 1.04-0.95 (m, 1H), 0.52-0.40 (m, 2H), 0.11 (dtt, J = 14.2, 9.5, 4.8 Hz, 2H). ¹³C NMR (101 MHz, CDCl₃) δ 171.89, 168.88, 163.16 (d, J = 245.6 Hz), 162.30, 159.45, 158.48 (d, J = 9.7 Hz), 146.62, 141.64, 137.49, 129.07 (d, J = 10.0 Hz), 122.60 (d, J = 3.5 Hz), 109.70, 106.93 (d, J = 21.1 Hz), 98.49 (d, J = 25.7 Hz), 76.03, 73.93, 73.37, 56.26, 55.59, 47.97, 20.72, 18.42, 15.38, 10.64, 3.09, 2.70. 296 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.51 ([M + H]⁺) calcd for (d, J = 6.7 Hz, 1H), 8.33 (d, J = 5.4 C₂₇H₃₄FN₂O₉, Hz, 1H), 7.26-7.22 (m, 1H), 7.01 549.2243; found, (d, J = 5.5 Hz, 1H), 6.62-6.56 (m, 549.2239 2H), 6.24 (d, J = 4.1 Hz, 1H), 5.39-5.31 (m, 1H), 4.68 (p, J = 7.2 Hz, 1H), 3.91 (s, 3H), 3.83 (s, 3H), 2.39 (s, 3H), 1.41 (d, J = 7.2 Hz, 3H), 1.23 (s, 9H), 1.19 (d, J = 6.5 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 176.86, 171.78, 168.86, 163.44 (d, J = 246.4 Hz), 162.35, 159.48, 157.82 (d, J = 10.1 Hz), 146.64, 141.55, 137.54, 128.46 (d, J = 10.2 Hz), 120.81 (d, J = 2.9 Hz), 109.76, 106.94 (d, J = 21.4 Hz), 98.87 (d, J = 25.8 Hz), 71.93, 70.12, 56.28, 55.77, 47.92, 38.90, 27.12, 20.72, 18.53, 14.86. 297 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.50 ([M + H]⁺) calcd for (d, J = 6.4 Hz, 1H), 8.33 (d, J = 5.2 C₂₆H₃₀FN₂O₉, Hz, 1H), 7.29 (d, J = 7.4 Hz, 1H), 533.1930; found, 7.01 (d, J = 5.4 Hz, 1H), 6.60 (t, J = 533.1923. 9.5 Hz, 2H), 6.27 (d, J = 4.2 Hz, 1H), 5.39-5.31 (m, 1H), 4.70 (p, J = 7.3 Hz, 1H), 3.91 (s, 3H), 3.82 (s, 3H), 2.39 (s, 3H), 1.67 (ddd, J = 12.7, 8.1, 4.5 Hz, 1H), 1.40 (d, J = 7.2 Hz, 3H), 1.18 (d, J = 6.5 Hz, 3H), 1.04-0.95 (m, 2H), 0.89 (d, J = 2.7 Hz, 2H). ¹³C NMR (101 MHz, CDCl₃) δ 173.42, 171.83, 168.85, 163.45 (d, J = 246.3 Hz), 162.36, 159.48, 157.82 (d, J = 9.8 Hz), 146.64, 141.55, 137.53, 128.82 (d, J = 10.1 Hz), 120.67 (d, J = 3.2 Hz), 109.77, 106.95 (d, J = 21.4 Hz), 98.84 (d, J = 25.9 Hz), 71.79, 70.18, 56.28, 55.78, 47.95, 20.72, 18.50, 14.95, 12.99, 8.57, 8.55. 298 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.48 ([M + H]⁺) calcd for (s, 1H), 8.32 (d, J = 5.5 Hz, 1H), C₂₅H₃₀FN₂O₈, 7.39 (dd, J = 8.3, 7.0 Hz, 1H), 6.99 505.1981; found, (d, J = 5.5 Hz, 1H), 6.65 (td, J = 8.3, 505.1972 2.3 Hz, 1H), 6.59 (dd, J = 10.9, 2.4 Hz, 1H), 5.17 (p, J = 6.4 Hz, 1H), 4.82 (d, J = 5.9 Hz, 1H), 4.71-4.62 (m, 1H), 3.90 (s, 3H), 3.83 (s, 3H), 3.18 (dq, J = 9.1, 3.0 Hz, 1H), 2.39 (s, 3H), 1.35 (d, J = 7.1 Hz, 3H), 1.14 (d, J = 6.5 Hz, 3H), 0.69-0.62 (m, 1H), 0.56-0.47 (m, 1H), 0.47-0.40 (m, 1H), 0.35 (dt, J = 11.1, 5.8 Hz, 1H). ¹³C NMR (101 MHz, CDCl₃) δ 172.14, 168.87, 164.47, 164.18 (d, J = 228.4 Hz), 162.25, 162.03, 159.43, 158.30 (d, J = 9.8 Hz), 146.62, 141.70, 137.48, 129.32 (d, J = 9.8 Hz), 122.50 (d, J = 3.5 Hz), 109.68, 106.88 (d, J = 21.3 Hz), 98.83 (d, J = 25.8 Hz), 77.57, 73.17, 56.25, 55.66, 52.30, 47.98, 20.72, 18.72, 16.09, 6.26, 5.47. ¹⁹F NMR (376 MHz, CDCl₃) δ-111.93 (s). 299 HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 8.51 ([M + H]⁺) calcd for (d, J = 6.2 Hz, 1H), 8.33 (d, J = 5.4 C₂₅H₃₀FN₂O₈, Hz, 1H), 7.36 (dd, J = 8.3, 7.0 Hz, 505.1981; found, 1H), 7.00 (d, J = 5.4 Hz, 1H), 6.65 505.1982 (td, J = 8.3, 2.4 Hz, 1H), 6.59 (dd, J = 10.9, 2.3 Hz, 1H), 5.20-5.12 (m, 1H), 4.86 (d, J = 4.8 Hz, 1H), 4.72-4.63 (m, 1H), 3.91 (s, 3H), 3.82 (s, 3H), 3.25 (ddd, J = 9.0, 6.0, 2.9 Hz, 1H), 2.40 (s, 3H), 1.33 (d, J = 7.1 Hz, 3H), 1.16 (d, J = 6.4 Hz, 3H), 0.66-0.59 (m, 1H), 0.54 (ddd, J = 14.0, 6.6, 4.2 Hz, 1H), 0.39 (dtd, J = 14.4, 10.1, 4.3 Hz, 2H). ¹³C NMR (101 MHz, CDCl₃) δ 171.83, 168.88, 163.24 (d, J = 245.4 Hz), 162.29, 159.47, 158.23 (d, J = 9.5 Hz), 146.61, 141.61, 137.51, 129.22 (d, J = 10.0 Hz), 122.44 (d, J = 3.5 Hz), 109.72, 106.88 (d, J = 21.2 Hz), 98.64 (d, J = 25.8 Hz), 72.88, 56.27, 55.65, 52.44, 47.98, 20.73, 18.55, 14.83, 6.11, 5.74. ¹⁹F NMR (376 MHz, CDCl₃) δ-112.15 (s). *Cmpd. No.—Compound Number

TABLE 3 Biological Testing Rating Scale Rating Table for Fungal Pathogens % Control Rating >80 A ≤80 B Not Tested C ≤0 D

TABLE 4 Biological Activity - High Volume Cereal Activity at 100 ppm *Cmpd. PUCCRT* SEPTTR* No. 1 DP* 3 DC* 1 DP* 3 DC* 113 A B A A 114 A A A A 115 D A D B 116 D D D B 117 A A A A 118 A A A A 119 A A B A 120 A B A B 121 A B B A 122 A A A A 123 A B B B 124 A A A A 125 B D B B 126 B D D B 127 A A A A 128 A B D B 129 B B A B 130 C C C C 131 B B D B 132 A B B D 133 B D D D 134 A A A B 135 A D A A 136 D B B D 137 A A A A 138 A A B B 139 C C C C 140 B A D B 141 C C C C 142 A A B B 143 C C C C 144 A B A B 145 A B A A 146 A A A A 147 A B A A 148 A B B A 149 A A A A 150 A A A B 151 A A A B 152 A A A A 153 C C C C 154 A A A A 162 A A A A 163 A A A A 164 A A A A 165 A A A A 166 A A A A 167 A A A A 168 A A A A 169 A B A A 172 A A A A 173 A A A A 175 A A A B 176 A A A A 177 B D A A 178 A B A A 288 A A B A 289 A A A A 290 A A A A 291 B B D A *Cmpd. No.—Compound Number *PUCCRT -Wheat Brown Rust (Puccinia triticina) *SEPTTR-Wheat Leaf Blotch (Zymoseptoria tritici) *1 DP—1 Day Protectant *3 DC—3 Day Curative *ppm—Parts Per Million

TABLE 5 Biological Activity - Low Volume Cereal Activity at 121.5 g/Ha *Cmpd. PUCCRT* SEPTTR* No. 1 DP* 3 DC* 1 DP* 3 DC* 182 A A A A 183 A A A A 184 A A A A 185 A A A A 186 D D B B 187 A A A A 188 A A A A 189 A B B D 190 A B B D 191 A A D B 192 A A A B 193 A A B D 194 A B B D 195 A B A A 196 A B A A 197 A B A D 198 A B A D 199 A B A A 200 A B A A 201 A A A A 202 A B A A 203 A B A A 204 A A B A 205 A A A A 206 A B A A 207 A B A A 208 A B A A 209 A B A A 210 B B B B 211 D B D B 212 B A D B 213 A A D B 214 A B A A 215 B B B B 216 A B A A 217 A B A A 218 D D A B 219 A A A A 220 A A B A 221 A B A B 222 A A A A 223 A B A A 224 A A B B 225 A A B A 226 A A B B 227 A A B A 228 A A B A 229 D A D B 230 A A D A 231 D A D A 232 A A D A 233 A A A A 234 A B A A 235 A A A A 236 A A A A 237 A A A A 238 A A A A 239 A B A A 240 A B A A 241 A A A A 242 A A A A 243 A B A A 244 A B A A 245 A B A A 246 A A A A 247 A A A A 248 A A A A 249 A A A A 250 A A A A 251 A A A A 252 A A A A 253 A A A A 254 A A A A 255 A A A A 256 A A A A 257 A A A A 258 A A A A 259 A A A A 260 A A A A 261 A A A A 262 A A A A 263 A A A A 264 A D A A 265 A A A A 266 A B A A 267 B D A B 268 A A A A 269 A A A A 270 A A A A 271 A D A A 272 A A A A 273 A A A A 274 A B A A 275 A A A B 294 B B A A 295 A B A A 296 A D A A 297 D D D B 298 B A B D 299 A B A A *Cmpd. No.—Compound Number *PUCCRT-Wheat Brown Rust (Puccinia triticina) *SEPTTR-Wheat Leaf Blotch (Zymoseptoria tritici) *1 DP—1 Day Protectant *3 DC—3 Day Curative *g/H—Grams Per Hectare

TABLE 6 Biological Activity - High Volume Disease Control at 25 ppm *Cmpd. PHAKPA* No. 1 DP* 3 DC* 182 A B 183 B B 184 B B 185 B D 186 D D 187 A B 188 A B 202 A B 203 C C 204 A B 205 B B 206 C C 207 B B 220 A B 225 A B 228 A D 230 B B 233 A B 235 B B 236 A D 237 B B 238 B B 241 A D 242 A B 250 A B 255 A D 256 A D 259 A D 260 A B 261 A D 262 A D 264 B B 265 B D 266 B D 267 B B 268 B B 269 A B 270 B D 271 B B 272 B D 273 B D 274 B D 275 B D 294 B B 295 A B 296 B B 297 B B 298 A B 299 A B *Cmpd. No.—Compound Number *PHAKPA-Asian Soybean Rust (Phakopsora pachyrhizi) *1 DP—1 Day Protectant *3 DC—3 Day Curative

TABLE 7 Biological Activity - 1DP High Volume Disease Control at 100 ppm *Cmpd. No. ALTESO* CERCBE* COLLLA* LEPTNO* PYRIOR* RHYNSE* VENTIN* 183 B A A A A A B 185 B B C C C C B 186 B B C C C C B 187 B A A A A A C 202 D B B B B D C 205 B A A A A B C 207 D A A A A A A 235 B A A A A A B 236 B A B A A A A 237 B A B A A A B 238 A A B A A A A 250 D B A D B B C 252 D A A A A A B 255 D A A A A B B 256 B A A A A A C 259 D A A A A A B 260 D A A A A A B 263 D A A A A A B *Cmpd. No.—Compound Number *ALTESO-Tomato Early Blight (Alternaria solani) *CERCBE-Leaf Spot of Sugar Beets (Cercospora beticola) *COLLLA-Cucumber Anthracnose (Colletotricum lagenarium) *LEPTNO-Wheat Glume Blotch (Leptosphaeria nodorum) *PYRIOR-Rice Blast (Pyricularia oryzae) *RHYNSE-Barley Scald (Rhyncosporium secalis) *VENTIN-Apple Scab (Venturia inaequalis) *1DP—1 Day Protectant 

What is claimed is:
 1. A compound of Formula I

X is hydrogen or C(O)R₅; Y is hydrogen, C(O)R₅, or Q; Q is

R₁ and R₁₁ are independently chosen from hydrogen or alkyl, optionally substituted with 0, 1 or multiple R₈; alternatively, R₁ and R₁₁ may be taken together to form a 3-6 membered saturated or partially saturated carbocycle or heterocycle, optionally substituted with 0, 1 or multiple R₈; R₂ and R₁₂ are independently chosen from hydrogen or methyl; R₃ is chosen from aryl or heteroaryl, each optionally substituted with 0, 1 or multiple R₈; R₄ is chosen from alkyl, aryl, or acyl, each optionally substituted with 0, 1 or multiple R₈; R₅ is chosen from alkoxy or benzyloxy, each optionally substituted with 0, 1, or multiple R₈; R₆ is chosen from hydrogen, alkoxy, or halo, each optionally substituted with 0, 1, or multiple R₈; R₇ is chosen from hydrogen, C(O)R₉, or —CH₂OC(O)R₉; R₈ is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkoxy, or heterocyclyl, each optionally substituted with 0, 1, or multiple R₁₀; R₉ is chosen from alkyl, alkoxy, or aryl, each optionally substituted with 0, 1, or multiple R₈; and R₁₀ is chosen from hydrogen, alkyl, aryl, acyl, halo, alkenyl, alkoxy, or heterocyclyl.
 2. A compound according to claim 1, wherein X and Y are hydrogen.
 3. A compound according to claim 2, wherein R₁ and R₁₁ are independently chosen from hydrogen or alkyl.
 4. A compound according to claim 2, wherein R₃ is aryl, optionally substituted with 0, 1 or multiple R₈.
 5. A compound according to claim 2, wherein R₄ is chosen from alkyl or aryl, each optionally substituted with 0, 1 or multiple R₈.
 6. A compound according to claim 2, wherein R₁ and R₁₁ are independently chosen from hydrogen or alkyl, R₃ is aryl, optionally substituted with 0, 1 or multiple R₈, and R₄ is chosen from alkyl or aryl, each optionally substituted with 0, 1 or multiple R₈.
 7. A compound according to claim 1, wherein X is C(O)R₅ and Y is hydrogen.
 8. A compound according to claim 7, wherein R₁ and R₁₁ are independently chosen from hydrogen or alkyl.
 9. A compound according to claim 7, wherein R₃ is aryl, optionally substituted with 0, 1 or multiple R₈.
 10. A compound according to claim 7, wherein R₄ is chosen from alkyl or aryl, each optionally substituted with 0, 1 or multiple R₈.
 11. A compound according to claim 7, wherein R₁ and R₁₁ are independently chosen from hydrogen or alkyl, R₃ is aryl, optionally substituted with 0, 1 or multiple R₈, and R₄ is chosen from alkyl or aryl, each optionally substituted with 0, 1 or multiple R₈.
 12. A compound according to claim 1, wherein X is hydrogen and Y is Q.
 13. A compound according to claim 12, wherein R₇ is hydrogen.
 14. A compound according to claim 13, wherein R₆ is alkoxy.
 15. A compound according to claim 14, wherein R₁ and R₁₁ are independently chosen from hydrogen or alkyl.
 16. A compound according to claim 14, wherein R₃ is aryl, optionally substituted with 0, 1 or multiple R₈.
 17. A compound according to claim 14, wherein R₄ is chosen from alkyl or aryl, each optionally substituted with 0, 1 or multiple R₈.
 18. A compound according to claim 14, wherein R₁ and R₁₁ are independently chosen from hydrogen or alkyl, R₃ is aryl, optionally substituted with 0, 1 or multiple R₈; and R₄ is chosen from alkyl or aryl, each optionally substituted with 0, 1 or multiple R₈.
 19. A compound according to claim 12, wherein R₇ is chosen from —C(O)R₉, or —CH₂OC(O)R₉.
 20. A compound according to claim 19, wherein R₉ is alkyl, optionally substituted with 0, 1 or multiple R₈.
 21. A compound according to claim 20, wherein R₁ and R₁₁ are independently chosen from hydrogen or alkyl.
 22. A compound according to claim 20, wherein R₃ is aryl, optionally substituted with 0, 1 or multiple R₈.
 23. A compound according to claim 20, wherein R₄ is chosen from alkyl or aryl, each optionally substituted with 0, 1 or multiple R₈.
 24. A compound according to claim 20, wherein R₁ and R₁₁ are independently chosen from hydrogen or alkyl, R₃ is aryl, optionally substituted with 0, 1 or multiple R₈; and R₄ is chosen from alkyl or aryl, each optionally substituted with 0, 1 or multiple R₈.
 25. A compound according to claim 24, wherein R₉ is chosen from —CH₃, —CH₂OCH₂CH₃, —CH₂CH₂OCH₃, —CH(CH₃)₂, —CH₂CH₂CH₂CH₃, or -cyclopropyl. 